AGROCHEMICAL COMPOSITION WITH IMPROVED DRIFT, UPTAKE AND RAINFASTNESS PROPERTIES

The present invention relates to agrochemical compositions: their use for foliar application; their use at low spray volumes; their use by unmanned aerial systems (UAS), unmanned guided vehicles (UGV), and tractor mounted boom sprayers fitted with conventional nozzles but also pulse width modulation spray nozzles or rotating disc droplet applicators; and their application for controlling agricultural pests, weeds or diseases, in particular on waxy leaves, and in particular the present invention relates to agrochemical compositions with a reduced drift, in particular in spray applications.

Skip to: Description  ·  Claims  · Patent History  ·  Patent History
Description

The present invention relates to agrochemical compositions: their use for foliar application; their use at low spray volumes; their use by unmanned aerial systems (UAS), unmanned guided vehicles (UGV), and tractor mounted boom sprayers fitted with conventional nozzles but also pulse width modulation spray nozzles or rotating disc droplet applicators; and their application for controlling agricultural pests, weeds or diseases, in particular on waxy leaves, and in particular the present invention relates to agrochemical compositions with a reduced drift, in particular in spray applications.

Pesticidal active compounds (AIs), e.g., herbicides, fungicides, insecticides, bactericides, miticides, plant growth regulators, etc., and their formulated products are often sprayed, usually after dilution in an aqueous spray liquid, onto plants and/or their habitat.

While modern agriculture faces many challenges in producing sufficient food in a safe and sustainable way, there is also a need to utilise crop protection products to enhance the safety, quality and yield while minimising the impact to the environment and agricultural land. Many crop protection products, whether chemical or biological, are normally applied at relatively high spray volumes, for example in selected cases >50 L/ha, and often >150-400 L/ha. A consequence of this is that much energy must be expended to carry the high volume of spray liquid and then apply it to the crop by spray application.

This can be performed by large tractors which on account of their weight and also the weight of the spray liquid produce CO2 from the mechanical work involved and also cause detrimental compaction of the soil, affecting root growth, health and yield of the plants, as well as the energy subsequently expended in remediating these effects.

Moreover, when applying such spray formulations, a more or less pronounced drifting of the spray solution containing the active substance(s) may be observed, depending on the wind conditions, nozzle type, and other application parameters such as, for example, nozzle pressure, boom height, and tractor speed.

Pesticide spray drift is a major source of concern in relation to the environmental impact of agriculture on natural ecosystems and urban areas. Furthermore, this drift is undesirable because it causes a certain part of the applied agrochemical to be lost as far as the intended application rate of the treated area is concerned.

More importantly, the drifting material might cause damage to neighbouring crops and especially, have effects on the local environment (e.g., surface water, non-target flora and fauna) as well as bystanders and occupants in residential areas.

There is a need for a solution that significantly reduces the drift of the active ingredients/formulations, both when sprayed, while at the same time preferably reducing high volumes of spray liquid and reducing the weight of the equipment required to apply the product.

Various methods are used to prevent the drifting of the spray outside the field borders. The use of natural or artificial windbreaks is well known. However, it has been described that even when such screens are used, drift can cause deposition of the active substances behind such borders (e.g., “Deposition of spray drift behind border structures”, M. De Schampheleire et al. Crop Protection 28 (2009) 1061-1075).

Another frequently used drift mitigation measure is buffer zones, either off-crop or in-crop. A disadvantage of off-crop buffer zones is that part of the field cannot be sown with a crop, an economic cost to the farmer. A disadvantage of in-crop buffer zones is that part of the crop is not protected adequately, resulting in a lower yield and perhaps resistance development. Clearly, this is something farmers want to prevent.

Next to physically limiting spray drift, it is also possible to alter the structure of the spray cloud so that less drops are prone to drift—i.e., typically those drops prone to drift have a diameter under 100 μm. This can be done by choosing different types of nozzles, changing the pressure at which the spray cloud is produced, or by changing the properties of the spray liquid itself. Especially changing nozzles and/or nozzle pressure is something farmers do not prefer to do because it is time consuming and makes the production of their crop more expensive. Also, the equipment necessary on sprayer to deal with variable application rates is not common. For these reasons, a more acceptable way to optimise a spray cloud, so that it leads to less or more limited drift, is by adjusting the properties of the spray liquid.

Although other factors such as meteorological conditions and spray boom height contribute to the potential for drift, spray droplet size distribution has been found to be a predominant factor. Teske et. al. (Teske M. E., Hewitt A. J., Valcore, D. L. 2004. The Role of Small Droplets in Classifying Drop Size Distributions ILASS Americas 17th Annual Conference: Arlington VA) have reported a value of <156 microns (μm) as the fraction of the spray droplet distribution that contributes to drift. Other researchers consider droplets with diameter <150 μm to be most drift-prone (J. H. Combellack, N. M. Westen and R. G. Richardson, Crop Prot., 1996, 15, 147-152, O. Permin, L. N. Jørgensen and K. Persson, Crop Prot., 1992, 11, 541-546). Another group H. Zhu, R. W. Dexter, R. D. Fox, D. L. Reichard, R. D. Brazee and H. E. Ozkan, J. Agric. Engineering Res., 1997, 67, 35-45.) cites a value of <200 μm as the driftable fraction. Based on theoretical studies and computer simulations, spray droplets with diameter <100 μm have been identified as the most drift-prone (H. Holterman, Kinetics and evaporation of water drops in air, 2003, IMAG Report 2003-12; P. A. Hobson, P. C. H. Miller, P. J. Walklate, C. R. Tuck and N. M. Western, J. Agr. Eng. Res., 1993, 54, 293-305; P. C. H. Miller, The measurement of spray drift, Pesticide Outlook, 2003, 14, 205-209). A good estimation of droplet size likely to contribute to drift, therefore, is the fraction below about 100 μm (driftable fraction). The smaller the droplets the longer is the residence time in the air and the higher is the tendency to evaporate and/or to drift rather than deposit within the field borders. A way to minimize the drift effect is by adding suitable drift control agents to pesticide formulations that increase the size of the droplets in the spray cloud—i.e., shift the droplet spectra towards larger droplets. When searching for solutions to overcome the drift problem, it has to be taken into account that the biological performance of the resulting application is not reduced. The use of formulation (both in-can and tank-mix) that increase the spray droplet size may reduce the efficacy to some extent, mainly because of reduced cover (e.g., “Biological efficacy of herbicides and fungicides applied with low-drift and twin-fluid nozzles” P. K. Jensen et al. Crop Protection 20 (2001)57-64). Retention of larger droplets on leaf surfaces can be reduced as they run-off or bounce or shatter and redistribute. Fewer larger droplets adhering to the leaf surface can reduce overall biological efficacy. Furthermore, for crops where the spray cloud has to penetrate into the canopy of the crop, very large droplets can pass directly through canopies, or bounce off leaves, or shatter and redistribute to soil. All these effects of applying active compound in large droplets may add to reduced efficacy.

It also has to be taken into account that many compounds added to a formulation to improve efficacy, storage, rainfastness and other important properties often have a negative effect on drift properties of the spray broth, i.e. tend to reduce droplet size or enhance evaporation afterwards.

Moerover, in agriculture, low spray volume application technologies including unmanned aerial systems (UAS), unmanned guided vehicles (UGV), and tractor mounted boom sprayers fitted with pulse width modulation spray nozzles or rotating disc droplet applicators are offering farmers solutions to apply products with low spray volumes, typically down to 10 to 20 l/ha or less. These solutions have advantages including for example that they require significantly less water which is important in regions where the supply of water is limited, require less energy to transport and apply the spray liquid, are faster both from quicker filling of the spray tank and faster application, reduce the CO2 generation from both the reduced volume of spray liquid to transport and from the use of smaller and lighter vehicles, reduced soil compaction damage, and enabling the use of cheaper application systems.

However, Wang et al [Field evaluation of an unmanned aerial vehicle (UAV) sprayer: effect of spray volume on deposition and the control of pests and disease in wheat. Pest Management Science 2019 doi/epdf/10.1002/ps.5321] demonstrated that as the spray volume is decreased from 450 and 225 l/ha to 28.1, 16.8 and 9.0 l/ha, the coverage (% area), number of spray deposits per area, and diameter of the spray deposits as measured on water sensitive paper all decreased (see Table 3 in Wang et al, 2019). In parallel, the biological control efficacy for both wheat aphid control and powdery mildew control decreased at low spray volumes with the greatest decrease observed at 9.0 l/ha, followed by 16.8 l/ha (see FIGS. 6, 7 and 8 in Wang et al, 2019).

There is therefore a need to design formulation systems that overcome the reduction in the coverage and diameter of the spray deposits at low spray volumes even through the number of spray deposits per area is decreasing: as the spray volume decreases, the number of spray droplets per unit area decreases proportionately for the same spray droplet spectra size. This is especially necessary below 25 l/ha, more especially below 17 l/ha, and even more especially at 10 l/ha and below.

Moreover, due to an increase in concentration of adjuvants in the spray solution to enhance the uptake into the plant, there is a higher chance for wash-off of the spray solution due to the higher local concentration of adjuvants.

Also, higher concentrations of surfactants in low spray volume formulations and spray broths usually lead to a smaller droplet size which in turn increases drift.

Therefore, there is a need to provide formulations which, when sprayed not only at “normal” volumes (50-500 l/ha) but also at ultra-low spray volumes according to the present invention, show a good coverage of the crops to provide good biological efficacy while at the same time have a good or acceptable uptake and do not show a high wash-off.

The solution is provided by formulations according to claim 1 and specifically by formulations containing specific drift reducing agents in combination with selected uptake and rainfastness agents at specific concentrations. Such formulations provide minimized or at least maintained drift while simultaneously providing increased coverage and increased diameter of spray deposits at low spray volumes, while maintaining or improving uptake, biological efficacy and rainfastness. Furthermore, the increased coverage and increased diameter of spray deposits is comparable to the coverage obtained at normal higher spray volumes.

Moreover, the formulations exemplifying the invention are particularly effective on hard to wet leaf surfaces where more conventional spray volumes have poor retention and coverage.

For low volume applications a particular advantage of the invention stemming from the low total amount of all ingredients compared to the level required at normal higher spray volumes is lower cost of formulations and their ease of production. Further advantages include improved formulation stability and simplified manufacture, less cost of goods as well as less impact on the environment.

Formulations, also for tank mixes, known in the prior art containing drift reducing agents are principally designed for much higher spray volumes and generally contain lower concentrations of uptake enhancing agents in the spray broth. Nevertheless, due to the high spray volumes used in the prior art, the total amount of agents used and therefore in the environment is higher than according to the present invention.

The concentration of the drift reducing agents is an important element of the invention, since in particular for oil based drift retardants, which also are used as penetration enhancers, suitable effects occur already at much lower concentrations then any effect on the penetration of actives. Thus, with low amounts of said oils and little impact on the environment drift can be reduced significantly. “Low amounts of said drift reducing agents (also referred to as drift retardants) means less than 25 g/l. This means, that already with an amount of 5 to 10 g/ha good drift reduction can be achieved instead of conventional 100-500 g/ha, which has to be present for an uptake effect.

On the other hand, high oil contents increase volume of product, manufacture complexity and can decrease product stability, thus they should be avoided if not necessary as uptake enhancer or solvent.

The minimum concentration of drift reducing agents is achieved, normally at 0.5. g/l.

With regard to the uptake agents in low volume applications, in a spray volume of 500 l/ha as it is used in the prior art, about 250 g/ha of uptake agents would be required to achieve suitable uptake. Hence, faced with the task to reduce the spray volume, the skilled person would apply the same concentration of uptake agents in the formulation. For example, for a spray volume of 10 l/ha about 5 g/ha (about 0.05% in the spray broth) uptake agent would be required. However, at such a low volume with such low concentration of uptake agents sufficient uptake cannot be achieved (see examples).

Moreover, as pointed out above, according to the present invention, while uptake enhancers have to be present to enable uptake of the active ingredients into the plants to enhance biological efficacy, at the same time a rain fastness additive has to be present to prevent wash-off in an intolerable amount.

As has been shown in prior applications, we have found that increasing the concentration of uptake agents as the spray volume decreases can compensate for the loss in coverage (due to increased uptake) from the reduction in spray volume. It was surprisingly found that for every reduction of the spray volume by 50%, the concentration of uptake agent should roughly be doubled.

Thus, although the absolute concentration of the uptake agents is increased compared to formulations known in the art, the relative total amount per ha can be decreased, which is advantageous, both economically and ecologically, while coverage by and efficacy of the formulation according to the invention is improved, maintained or at least kept at an acceptable level when other benefits of the low volume applications are considered, e.g. less costs of formulation due to less cost of goods, smaller vehicles with less working costs, less compacting of soil etc.

Further, we have surprisingly found that the formulations according to the present invention show low drift, and an comparable or enhanced uptake of active ingredient when compared to formulations without drift retardant agents known in the art.

It also has been found, that despite the high concentration of uptake agents (uptake enhancers), the rainfastness and drift reduction of the formulations according to the present invention is also comparable or better than those of the reference formulations based on the prior art.

Further, it was found that when methyl esters of vegetable oils are used as b), there is also a positive effect observed on foaming, i.e. a reduction of foam, of the formulation, in particular in connection with the organosilicone spreaders.

As pointed out above, the formulations of the present invention are particularly suited for low volume applications depending on the leaf surface texture. Bico et al [Wetting of textured surfaces, Colloids and Surfaces A, 206 (2002) 41-46] have established that compared to smooth surfaces, textured surfaces can enhance the wetting for formulation spray dilutions with contact angles <90° and reduce the wetting for contact angles >90°.

This is also the case for leaf surfaces, in particular textured leaf surfaces, when sprayed in a method according to the invention.

Textured leaf surfaces include leaves containing micron-scale wax crystals on the surface such as garlic, onions, leeks, soybean (≤GS 16 (BBCH 16)), oats, wheat, barley, rice, sugarcane, pineapple, banana, linseed, lilies, orchids, corn (≤GS 15 (BBCH 15)), cabbage, brussels sprouts, broccoli, cauliflower, rye, rapeseed, tulips and peanut for example, and leaves with surface textures such as lotus plant leaves for example.

The same is obviously true for the application on weeds with textured leaf surfaces, for example Cassia obtusifolia, Chenopodium album, Agropyron repens, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Brachiaria plantaginea, Bromus secalinus, Cynodon dactylon, Digitaria sanguinalis, Echinochloa crus-galli, Panicum dichotomiflorum, Poa annua, Setaria faberi and Sorghum halepense amongst others.

The surface texture can be determined by scanning electron microscope (SEM) observations and the In summary, the object of the present invention is to provide a formulation which can be applied in high (200-500 l/ha or even higher) to low volumes, i.e. <20 l/ha, while still providing good drift reduction, uptake and biological efficacy against fungicidal pathogens, weeds and pests, and providing good rainfastness, and at the same time reducing the amounts of additional additives applied per ha, as well as a method of using said formulation at high to low volumes (<20 l/ha), and the use of said formulation for application in low volumes as defined above.

While the application on textured leaves is preferred, surprisingly it was found that also on non-textured leaves the formulations according to the instant invention showed good results compared to classical spray application formulations for 200 l/h.

In one aspect, the present invention is directed to the use of the compositions according to the invention for foliar application.

If not otherwise indicated, % in this application means percent by weight (% w/w).

It is understood that in case of combinations of various components, the percentages of all components of the formulations always sum up to 100.

Further, if not otherwise indicated, the reference “to volume” for water indicates that water is added to a total volume of a formulation of 1000 ml (1l). For the sake of clarity it is understood that if unclear the density of the formulation is understood as to be 1 g/cm3.

In the context of the present invention aqueous based agrochemical compositions comprise at least 5% of water and include suspension concentrates, aqueous suspensions, suspo-emulsions or capsule suspensions, preferably suspension concentrates and aqueous suspensions.

Further, it is understood, that the preferred given ranges of the application volumes or application rates as well as of the respective ingredients as given in the instant specification can be freely combined and all combinations are disclosed herein, however, in a more preferred embodiment, the ingredients are preferably present in the ranges of the same degree of preference, and even more preferred the ingredients are present in the most preferred ranges.

It is further understood that the formulations of the instant invention do not refer to tank-mix formulations, but to ready to use (in-can) formulations, which can be used without further additions of adjuvants, like surfactant, wetters, uptake enhancers, drift or rainfastness tank-mix additives.

FIG. 1 shows spray deposits on wheat leaves. (i) and (iii) are at a spray dilution concentration of 10 l/ha, (ii) and (iv) are at a spray dilution concentration of 200 l/ha. (i) and (ii) are a reference recipe, (iii) and (iv) are a recipe illustrative of the invention. Images are taken from Example FN9.

FIG. 2 shows spray deposits on tomato plants at a spray dilution concentration of 15 l/ha, (i) is a reference recipe, (ii) is a recipe illustrative of the invention. Images are taken from Example FN10.

In one aspect, the invention refers to a formulation comprising:

    • a) One or more active ingredients,
    • b) One or more drift reducing agent
    • d) One or more uptake enhancing agents,
    • e) One or more rain-fast additives,
    • f) Other formulants,
    • g) one or more carriers to volume (1 L or 1 kg),
      • wherein in one preferred embodiment b) is a vegetable oil or a vegetable oil ester or diester and in another embodiment component b) is a polymeric drift reducing agent.

In another preferred embodiment b) is present in 0.01 to 50 g/l.

If not otherwise indicated in the present invention the carrier is usually used to volume the formulation. Preferably, the concentration of carrier in the formulation according to the invention is at least 5% w/w, more preferred at least 10% w/w such as at least 20% w/w, at least 40% w/w, at least 50% w/w, at least 60% w/w, at least 70% w/w and at least 80% w/w or respectively at least 50 g/l, more preferred at least 100 g/l such as at least 200 g/l, at least 400 g/l, at least 500 g/l, at least 600 g/l, at least 700 g/l and at least 800 g/l.

The formulation is preferably a spray application to be used on crops.

In a further preferred embodiment the formulation is a flowable formulation containing active ingredients in particulate form, in particular SC, SE and OD formulations. Most preferred the formulation is a SC formulation.

In a preferred embodiment according to the present invention, also for the following embodiments in the specification, the carrier is water.

In a preferred embodiment the formulation of the instant invention comprises

    • a) One or more active ingredients,
    • b) One or more drift reducing ingredients
    • d) One or more uptake enhancing agents,
    • e) One or more rain-fast additives,
    • f) Optional other formulants,
    • g) one or more carriers to volume,
      comprising the components a) to g) in the following amounts
    • a) from 5 to 500 g/l,
    • b) from 0.01 to 50 g/l, and in case of b) being an vegetable oil or ester from in 1 to 50 g/l, in case of b) being a drift reducing polymer in 0.05 to 3 g/l,
    • d) from 10 to 180 g/l,
    • e) from 5 to 150 g/l,
    • g) carrier to volume.

In a preferred embodiment the formulation of the instant invention comprises

    • a) One or more active ingredients,
    • b) One or more drift reducing ingredients
    • d) One or more uptake enhancing agents,
    • e) One or more rain-fast additives,
    • f1) At least one suitable non-ionic surfactant and/or suitable ionic surfactant.,
    • f2) Optionally, a rheological modifier,
    • f3) Optionally, a suitable antifoam substance,
    • f4) Optionally, suitable antifreeze agents,
    • f5) Optionally, suitable other formulants.
    • g) carrier to volume,
    • wherein b) is present in 0.01 to 50 g/l, and wherein water is even more preferred as carrier and wherein in one preferred embodiment b) is a vegetable oil or an vegetable oil ester or diester and in another embodiment component b) is a polymeric drift reducing agent.

In another embodiment at least one of f2, f3, f4 and f5 are mandatory, preferably, at least two of f1, f2, f3, f4 and f5 are mandatory, and in yet another embodiment f1, f2, f3, f4 and f5 are mandatory.

In a preferred embodiment component a) is preferably present in an amount from 5 to 500 g/l, preferably from 10 to 320 g/l, and most preferred from 20 to 230 g/l.

In an alternative embodiment component a) is a fungicide.

In an alternative embodiment component a) is an insecticide.

In an alternative embodiment component a) is a herbicide.

In a preferred embodiment component b) is present in 0.01 to 50 g/l, preferably from 0.1 to 30 g/l, and most preferred from 1 to 20 g/l.

In case b) is selected from the group of vegetable oils and esters, b) preferably is present in 1 to 50 g/l, preferably from 5 to 30 g/l, and most preferred from 6 to 30 g/l.

In case b) is selected from the group of polymeric drift reducing agents, b) preferably is present in 0.05 to 10 g/l, preferably from 0.1 to 8 g/l, and most preferred from 0.2 to 6 g/l.

In a preferred embodiment component d) is present in 10 to 180 g/l, preferably from 20 to 150 g/l, and most preferred from 30 to 140 g/l.

In a preferred embodiment component e) is present in 5 to 150 g/l, preferably from 10 to 100 g/l, and most preferred from 20 to 80 g/l.

In a preferred embodiment the one or more component f1) is present in 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferred from 10 to 80 g/l.

In a preferred embodiment the one or more component f2) is present in 0 to 60 g/l, preferably from 1 to 20 g/l, and most preferred from 2 to 10 g/l.

In a preferred embodiment the one or more component f) is present in 0 to 30 g/l, preferably from 0.5 to 20 g/l, and most preferred from 1 to 12 g/l.

In a preferred embodiment the one or more component f4) is present in 0 to 200 g/l, preferably from 5 to 150 g/l, and most preferred from 10 to 120 g/l.

In a preferred embodiment the one or more component f5) is present in 0 to 200 g/l, preferably from 0.1 to 120 g/l, and most preferred from 0.5 to 80 g/l.

In one embodiment the formulation comprises the components a) to f) in the following amounts

    • a) from 5 to 500 g/l, preferably from 10 to 320 g/l, and most preferred from 20 to 230 g/l,
    • b) from 0.01 to 50 g/l, preferably from 0.1 to 30 g/l, and most preferred from 1 to 20 g/l, and in case of b) being an vegetable oil or ester from in 1 to 50 g/l, preferably from 5 to 30 g/l, and most preferred from 6 to 30 g/l, in case of b) being a drift reducing polymer in 0.05 to 10 g/l, preferably from 0.1 to 8 g/l, and most preferred from 0.2 to 6 g/l.
    • d) from 10 to 180 g/l, preferably from 20 to 150 g/l, and most preferred from 30 to 140 g/l,
    • e) from 5 to 150 g/l, preferably from 10 to 100 g/l, and most preferred from 20 to 80 g/l,
    • f) from 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferred from 10 to 80 g/l.
    • g) carrier to volume.

In another embodiment the formulation comprises the components a) to f) in the following amounts

    • a) from 5 to 500 g/l, preferably from 10 to 320 g/l, and most preferred from 20 to 230 g/l,
    • b) from 0.01 to 50 g/l, preferably from 0.1 to 30 g/l, and most preferred from 1 to 20 g/l, and in case of b) being an vegetable oil or ester from in 1 to 50 g/l, preferably from 5 to 30 g/l, and most preferred from 6 to 30 g/l, in case of b) being a drift reducing polymer in 0.05 to 10 g/l, preferably from 0.1 to 8 g/l, and most preferred from 0.2 to 6 g/l.
    • d) from 10 to 180 g/l, preferably from 20 to 150 g/l, and most preferred from 30 to 140 g/l,
    • e) from 5 to 150 g/l, preferably from 10 to 100 g/l, and most preferred from 20 to 80 g/l,
    • f1) from 4 to 250 g/l, preferably from 8 to 120 g/l, and most preferred from 10 to 80 g/l,
    • f2) from 0 to 60 g/l, preferably from 1 to 20 g/l, and most preferred from 2 to 10 g/l,
    • f) from 0 to 30 g/l, preferably from 0.5 to 20 g/l, and most preferred from 1 to 12 g/l,
    • f4) from 0 to 200 g/l, preferably from 5 to 150 g/l, and most preferred from 10 to 120 g/l,
    • f5) from 0 to 200 g/l, preferably from 0.1 to 120 g/l, and most preferred from 0.5 to 80 g/l,
    • g) carrier to volume.

It is understood that in case a solid carrier is used, the above referenced amounts refer to 1 kg instead of to 1 l, i.e. g/kg.

As indicated above, component g) is always added to volume, i.e. to 1 l or 1 kg.

In a further preferred embodiment of the present invention the formulation consists only of the above described ingredients a) to g) in the specified amounts and ranges.

In a preferred embodiment the herbicide is used in combination with a safener, which is preferably selected from the group comprising isoxadifen-ethyl and mefenpyr-diethyl.

The instant invention further applies to a method of application of the above referenced formulations, wherein the formulation is applied at a spray volume of between 1 and 30 l/ha, preferably 1 and 20 l/ha, more preferred 2 and 15 l/ha, and most preferably 5 and 15 l/ha.

More preferred, the instant invention applies to a method of application of the above referenced formulations, wherein the formulation is applied at a spray volume of between 1 and 30 l/ha, preferably 1 and 20 l/ha, more preferred 2 and 15 l/ha, and most preferably 5 and 15 l/ha, and the amount of a) is present from 5 to 500 g/l, preferably from 10 to 320 g/l, and most preferred from 20 to 230 g/l, and even further preferred b) is present from 0.01 to 50 g/l, preferably from 0.1 to 30 g/l, and most preferred from 1 to 20 g/l, and in case of b) being an vegetable oil or ester from in 1 to 50 g/l, preferably from 5 to 30 g/l, and most preferred from 6 to 30 g/l, in case of b) being a drift reducing polymer in 0.05 to 10 g/l, preferably from 0.1 to 8 g/l, and most preferred from 0.2 to 6 g/l, and further preferred d) is present in an amount from 10 to 180 g/l, preferably from 20 to 150 g/l, and most preferred from 30 to 140 g/l, and even further preferred e) is present in an amount from from 5 to 150 g/l, preferably from 10 to 100 g/l, and most preferred from 20 to 80 g/1.

In another aspect the instant invention applies to a method of application of the above referenced formulations,

    • wherein the formulation is applied at a spray volume of between 1 and 30 l/ha, preferably 1 and 20 l/ha, more preferred 2 and 15 l/ha, and most preferably 5 and 15 l/ha, and
    • wherein preferably the applied amount of a) to the crop is between 2 and 150 g/ha, preferably between and 120 g/ha, and more preferred between 20 and 100 g/ha.

Further, the drift reducing agent b) in case of b) being a vegetable oil or ester of an vegetable oil is preferably applied from 0.1 g/ha to 50 g/ha, more preferably from 1 g/ha to 40 g/ha, and most preferred from 5 g/ha to 30 g/ha.

Further, the drift reducing agent b) in case of b) being a polymer is preferably applied from 0.01 g/ha to 25 g/ha, more preferably from 0.05 g/ha to 10 g/ha, and most preferred from 0.1 g/ha to 6 g/ha.

In contrast to the aforementioned oils as drift reducing agents the corresponding polymers have to be present in higher concentrations in the instant formulation in case they shall be sprayed later at higher spray volumes, since dilution has a stronger effect on those.

Further, the uptake agent d) is preferably applied from 5 g/ha to 150 g/ha, more preferably from 7.5 g/ha to 100 g/ha, and most preferred from 10 g/ha to 60 g/ha.

In one embodiment, the with the above indicated method applied amount of a) to the crop is between 2 and 10 g/ha.

In another embodiment, the with the above indicated method applied amount of a) to the crop is between and 110 g/ha.

In one embodiment in the applications described above, the active ingredient (ai) a) is preferably applied from 2 and 150 g/ha, preferably between 5 and 120 g/ha, and more preferred between 20 and 100 g/ha, while correspondingly the uptake agent is preferably applied from 10 g/ha to 100 g/ha, more preferably from 20 g/ha to 80 g/ha, and most preferred from 40 g/ha to 60 g/ha.

In particular the formulations of the instant invention are useful for application with a spray volume of between 1 and 20 l/ha, preferably 2 and 15 l/ha, more preferably 5 and 15 l/ha on plants or crops with textured leaf surfaces, preferably on wheat, barley, rice, rapeseed, soybean (young plants) and cabbage.

Further, the instant invention refers to a method of treating crops with textured leaf surfaces, preferably wheat, barley, rice, rapeseed, soybean (young plants) and cabbage, with a spray volume of between 1 and 20 l/ha, preferably 2 and 15 l/ha, more preferably 5 and 15 l/ha.

In a preferred embodiment the above described applications are applied on crops with textured leaf surfaces, preferably on wheat, barley, rice, rapeseed, soybean (young plants) and cabbage.

In one embodiment the active ingredient is a fungicide or a mixture of two fungicides or a mixture of three fungicides.

In another embodiment the active ingredient is an insecticide or a mixture of two insecticides or a mixture of three insecticides.

In yet another embodiment the active ingredient is a herbicide or a mixture of two herbicides or a mixture of three herbicides, wherein preferably in the mixtures on mixing partner is a safener.

In one embodiment the concentration of the additives b) to e) in the spray liquid of the agrochemical composition as described herein is from

    • Additive b) from 0.005 to 1 g/l, and most preferred from 0.04 to 0.6 g/l where b) is a polymer
    • Additive b) from 0.01 to 5 g/l, and most preferred from 0.02 to 2.5 g/l where b) is an oil
    • Additive d) from 1 to 20 g/l, and most preferred from 2 to 8 g/l
    • Additive e) from 0.5 to 10 g/l, and most preferred from 2 to 6 g/l

In one embodiment the) dose of the additives b) to e) per ha in the spray liquid of the agrochemical composition as described herein the is from

    • Additive b) from 0.05 to 10 g/ha, and most preferred from 0.4 to 6 g/ha where b) is a polymer
    • Additive b) from 0.1 to 50 g/ha, and most preferred from 0.2 to 30 g/ha where b) is an oil
    • Additive d) from 10 to 200 g/ha, and most preferred from 40 to 80 g/ha
    • Additive e) from 5 to 100 g/ha, and most preferred from 20 to 60 g/ha

In one embodiment the concentration in the formulation, the concentration in the spray liquid and the dose of the additives b) to e) per ha is combined in the following way

    • Additive b) from 0.4 to 6 g/l in the formulation, from 0.02 to 0.6 g/l in the spray liquid and from 0.2 to 6 g/ha where b) is a polymer
    • Additive b) from 0.1 to 50 g/l in the formulation, from 0.01 to 5 g/l in the spray liquid and from 0.2 to 30 g/ha where b) is an oil
    • Additive d) from 40 to 160 g/l in the formulation, from 2 to 8 g/l in the spray liquid and from 40 to 80 g/ha
    • Additive e) from 20 to 80 g/l in the formulation, from 1 to 6 g/l in the spray liquid and from 20 to 60 g/ha

The corresponding doses of uptake agent (d) in formulations according to the invention to the applied doses are:

    • A 2 l/ha liquid formulation delivering
      • 50 g/ha of uptake agent contains 25 g/l of uptake enhancer (d).
      • 30 g/ha of uptake agent contains 15 g/l of uptake enhancer (d).
      • 12 g/ha of uptake agent contains 6 g/l of uptake enhancer (d).
      • 10 g/ha of uptake agent contains 5 g/l of uptake enhancer (d).
    • A 1 l/ha liquid formulation delivering:
      • 50 g/ha of uptake agent contains 50 g/l of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 30 g/l of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 12 g/l of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 10 g/l of uptake enhancer (d).
    • A 0.5 l/ha liquid formulation delivering:
      • 50 g/ha of uptake agent contains 100 g/l of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 60 g/l of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 24 g/l of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 20 g/l of uptake enhancer (d).
    • A 0.2 l/ha liquid formulation delivering:
      • 50 g/ha of uptake agent contains 250 g/l of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 150 g/l of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 60 g/l of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 50 g/l of uptake enhancer (d).
    • A 2 kg/ha solid formulation delivering:
      • 50 g/ha of uptake agent contains 25 g/kg of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 15 g/kg of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 6 g/kg of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 5 g/kg of uptake enhancer (d).
    • A 1 kg/ha solid formulation delivering:
      • 50 g/ha of uptake agent contains 50 g/kg of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 30 g/kg of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 12 g/kg of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 10 g/kg of uptake enhancer (d).
    • A 0.5 kg/ha solid formulation delivering:
      • 50 g/ha of uptake agent contains 100 g/kg of uptake enhancer (d),
      • 30 g/ha of uptake agent contains 60 g/kg of uptake enhancer (d),
      • 12 g/ha of uptake agent contains 24 g/kg of uptake enhancer (d),
      • 10 g/ha of uptake agent contains 20 g/kg of uptake enhancer (d).

The concentrations of uptake agent (d) in formulations that are applied at other dose per hectare rates can be calculated in the same way.

In the context of the present invention, suitable formulation types are by definition suspension concentrates, aqueous suspensions, suspo-emulsions or capsule suspensions, emulsion concentrates, water dispersible granules, oil dispersions, emulsifiable concentrates, dispersible concentrates, wettable granules, preferably suspension concentrates, aqueous suspensions, suspo-emulsions and oil dispersions, wherein in the case of non-aqueous formulations or solid formulations the sprayable formulation are obtained by adding water.

Active Ingredients (a):

The active compounds identified here by their common names are known and are described, for example, in the pesticide handbook (“The Pesticide Manual” 16th Ed., British Crop Protection Council 2012) or can be found on the Internet (e.g. http://www.alanwood.net/pesticides). The classification is based on the current IRAC Mode of Action Classification Scheme at the time of filing of this patent application.

Examples of fungicides (a) according to the invention are:

    • 1) Inhibitors of the ergosterol biosynthesis, for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031) (2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chloro-cyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichloro-phenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluoro-phenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N′-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N′-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N′-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N′-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N′-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]-phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N′-(2,5-dimethyl-4-{3-[(2,2,2-trifluoro-ethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N′-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N′-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071) N′-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072) N′-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N′-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N′-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimido-formamide, (1.075) N′-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N′-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N′-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N′-{5-bromo-6-[(cis-4-isopropyl-cyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N′-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N′-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimido-formamide, (1.081) ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1.086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, (1.087)N-isopropyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylimidoformamide, (1.088) N′-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimido-formamide, (1.089) hexaconazole, (1.090) penconazole, (1.091) fenbuconazole.
    • 2) Inhibitors of the respiratory chain at complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid, (2.021) 50 sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)-pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034)N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035)N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036)N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037)N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039)N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040)N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041)N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042)N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043)N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044)N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050)N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051)N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052)N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053)N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054)N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055)N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056)N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne, (2.058)N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)-nicotinamide, (2.059)N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.
    • 3) Inhibitors of the respiratory chain at complex III, for example (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-50 methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamid, (3.026) mandestrobin, (3.027)N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid.
    • 4) Inhibitors of the mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) pyridachlometyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023)N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024)N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025)N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.026) fluopimomide.
    • 5) Compounds capable to have a multisite action, for example (5.001) bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3′,4′:5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.
    • 6) Compounds capable to induce a host defence, for example (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil.
    • 7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.
    • 8) Inhibitors of the ATP production, for example (8.001) silthiofam.
    • 9) Inhibitors of the cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.
    • 10) Inhibitors of the lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
    • 11) Inhibitors of the melanin biosynthesis, for example (11.001) tricyclazole, (11.002) tolprocarb.
    • 12) Inhibitors of the nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
    • 13) Inhibitors of the signal transduction, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
    • 14) Compounds capable to act as an uncoupler, for example (14.001) fluazinam, (14.002) meptyldinocap.
    • 15) Further fungicides selected from the group consisting of (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salts, (15.025) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)-phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoro-methyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiprolin, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N‘-phenyl-N’-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]-pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N′-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimido-formamide), (15.065) (N′-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074) methyl {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.077)N-[(E)-methoxyimino-methyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078)N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079)N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080)N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082)N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083)N-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoro-methyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084)N-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087)N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide, (15.088) 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089)N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1-methoxy-1-methyl-3-[[4-[5-(trifluoro-methyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092)N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phen-yl]methyl]propanamide, (15.093)N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]cyclopropanecarboxamide, (15.094) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095)N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097)N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoro-methyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]isooxazolidin-3-one, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenyl]methyl]azepan-2-one, (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenyl]methyl]isoxazolidin-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) ethyl 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylate, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110)N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111)N-(1-methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112)N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113) 1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydro-isoquinoline, (15.115) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethyl-carbamate, (15.118)N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.119) 3-[2-(1-{[5 -methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.121) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.123) 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.124) 8-fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl)quinoline-3-carboxamide, (15.125) 8-fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.126)N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide and (15.127)N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide.

Examples of insecticides (a) according to the invention are:

    • (1) Acetylcholinesterase(AChE)-inhibitors, e.g. Carbamates Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC andan Xylylcarb, or organophosphates, e.g. Acephat, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos/DDVP, Dicrotophos, Dimethoat, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazat, Heptenophos, Imicyafos, Isofenphos, Isopropyl-O-(methoxyaminothio-phosphoryl)salicylat, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion-methyl, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon andand Vamidothion.
    • (2) GABA-gated chloride channel antagonists, preferably Cyclodien-organochlorine selected from the group of Chlordan and Endosulfan, or Phenylpyrazole (Fiprole) selected from Ethiprol and Fipronil.
    • (3) Sodium channel modulators/voltage-dependent sodium channel blockers, for example pyrethroids, e.g. Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, lambda-Cyhalothrin, gamma-Cyhalothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyphenothrin [(1R)-trans isomers], Deltamethrin, Empenthrin [(EZ)-(1R) isomers), Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, tau-Fluvalinate, Halfenprox, Imiprothrin, Kadethrin, Momfluorothrin, Permethrin, Phenothrin [(1R)-trans isomer), Prallethrin, Pyrethrine (pyrethrum), Resmethrin, Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R) isomers)], Tralomethrin and Transfluthrin or DDT or Methoxychlor.
    • (4) Nicotinic acetylcholine receptor (nAChR) competitive activators, preferably Neonicotinoids selected from Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid and Thiamethoxam, or Nicotin, or Sulfoximine selected from Sulfoxaflor, or Butenolide selected from Flupyradifurone, or Mesoionics selected from Triflumezopyrim.
    • (5) Nicotinic acetylcholine receptor (nAChR) allosteric activators, preferably Spinosynes selected from Spinetoram and Spinosad.
    • (6) Allosteric modulators of the glutamate-dependent chloride channel (GluCl), preferablyAvermectine/Milbemycine selected from Abamectin, Emamectin-benzoate, Lepimectin and Milbemectin.
    • (7) Juvenile hormone mimetics, preferably Juvenile hormon-analogs selected from Hydropren, Kinopren and Methopren, or Fenoxycarb or Pyriproxyfen.
    • (8) Various non-specific (multi-site) inhibitors, preferably Alkylhalogenides selected from Methylbromide and other Alkylhalogenides, or Chloropicrin or Sulfurylfluorid or Borax or Tartar emetic or Methylisocyanate generators selected from Diazomet and Metam.
    • (9) TRPV channel modulators of chordotonal organs selected from Pymetrozin and Pyrifluquinazon.
    • (10) Mite growth inhibitors selected from Clofentezin, Hexythiazox, Diflovidazin and Etoxazol.
    • (11) Microbial disruptors of the insect intestinal membrane selected from Bacillus thuringiensis Subspezies israelensis, Bacillus sphaericus, Bacillus thuringiensis Subspezies aizawai, Bacillus thuringiensis Subspezies kurstaki, Bacillus thuringiensis subspecies tenebrionis and B.t.-plant proteins selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, VIP3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1/35Ab1.
    • (12) Mitochondrial ATP synthase inhibitors, preferably ATP-disruptors selected from Diafenthiuron, or Organo-tin-compoiunds selected from Azocyclotin, Cyhexatin and Fenbutatin-oxid, or Propargit or Tetradifon.
    • (13) Decoupler of oxidative phosphorylation by disturbance of the proton gradient selected from Chlorfenapyr, DNOC and Sulfluramid.
    • (14) Nicotinic acetylcholine receptor channel blocker selected from Bensultap, Cartap-hydrochlorid, Thiocyclam and Thiosultap-Sodium.
    • (15) Inhibitors of chitin biosynthesis, Typ 0, selected from Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron and Triflumuron.
    • (16) Inhibitors of chitin biosynthesis, Typ 1 selected from Buprofezin.
    • (17) Molting disruptor (especially dipteras, i.e. two-winged insects) selected from Cyromazin.
    • (18) Ecdyson receptor agonists selected from Chromafenozid, Halofenozid, Methoxyfenozid and Tebufenozid.
    • (19) Octopamin-receptor-agonists selected from Amitraz.
    • (20) Mitochondrial complex III electron transport inhibitors selected from Hydramethylnon, Acequinocyl and Fluacrypyrim.
    • (21) Mitochondrial complex I electron transport inhibitors, preferably so-called METI-acaricides selected from Fenazaquin, Fenpyroximat, Pyrimidifen, Pyridaben, Tebufenpyrad and Tolfenpyrad, or Rotenon (Derris).
    • (22) Blocker of the voltage-dependent sodium channel selected from Indoxacarb and Metaflumizone.
    • (23) Inhibitors of acetyl-CoA carboxylase, preferably tetronic and tetramic acid derivatives selected from Spirodiclofen, Spiromesifen, Spirotetramat and Spidoxamate (IUPAC Name: 11-(4-chloro-2,6-xylyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one).
    • (24) Mitochondrial complex IV electron transport inhibitors, preferably Phosphines selected from Aluminiumphosphid, Calciumphosphid, Phosphin and Zinkphosphid, or Cyanides selected from Calciumcyanid, Potassiumcyanid and Sodiumcyanid.
    • (25) Mitochondrial complex II electron transport inhibitors, preferablybeta-Ketonitrilderivate selected from Cyenopyrafen and Cyflumetofen, or Carboxanilide selected from Pyflubumid.
    • (28) Ryanodinreceptor-modulators, preferably Diamide selected from Chlorantraniliprol, Cyantraniliprol and Flubendiamid.
    • (29) Modulators of chordotonal organs (with undefined target structure) selected from Flonicamid.
    • (30) other active ingredients selected from Acynonapyr, Afidopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximat, Benzpyrimoxan, Bifenazat, Broflanilid, Bromopropylat, Chinomethionat, Chloroprallethrin, Cryolit, Cyclaniliprol, Cycloxaprid, Cyhalodiamid, Dicloromezotiaz, Dicofol, Dimpropyridaz, epsilon-Metofluthrin, epsilon-Momfluthrin, Flometoquin, Fluazaindolizin, Fluensulfon, Flufenerim, Flufenoxystrobin, Flufiprol, Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fluxametamid, Fufenozid, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, Isocycloseram, kappa-Bifenthrin, kappa-Tefluthrin, Lotilaner, Meperfluthrin, Oxazosulfyl, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Spirobudiclofen, Spiropidion, Tetramethylfluthrin, Tetraniliprol, Tetrachlorantraniliprol, Tigolaner, Tioxazafen, Thiofluoximat and Iodmethan; products from Bacillus firmus (I-1582, BioNeem, Votivo), as well as following compounds: 1-{2-Fluor-4-methyl-5-[(2,2,2-trifluorethyl)sulfinyl]phenyl}-3-(trifluormethyl)-1H-1,2,4-triazol-5-amin (known from WO2006/043635) (CAS 885026-50-6), {1′-[(2E)-3-(4-Chlorphenyl)prop-2-en-1-yl]-5-fluorspiro[indol-3,4′-piperidin]-1(2H)-yl}(2-chlorpyridin-4-yl)methanon (known from WO2003/106457) (CAS 637360-23-7), 2-Chlor-N-[2-{1-[(2E)-3-(4-chlorphenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluormethyl)phenyl]isonicotinamid (known from WO2006/003494) (CAS 872999-66-1), 3-(4-Chlor-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-on (known from WO 2010052161) (CAS 1225292-17-0), 3-(4-Chlor-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-ethylcarbonat (known from EP 2647626) (CAS-1440516-42-6), 4-(But-2-in-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidin (known from WO2004/099160) (CAS 792914-58-0), PF1364 (known from JP2010/018586) (CAS-Reg. No. 1204776-60-2), (3E)-3-[1-[(6-Chlor-3-pyridyl)methyl]-2-pyridyliden]-1,1,1-trifluorpropan-2-on (known from WO2013/144213) (CAS 1461743-15-6), N-[3-(Benzylcarbamoyl)-4-chlorphenyl]-1-methyl-3-(pentafluorethyl)-4-(trifluormethyl)-1H-pyrazol-5-carboxamid (known from WO2010/051926) (CAS 1226889-14-0), 5-Brom-4-chlor-N-[4-chlor-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chlor-2-pyridyl)pyrazol-3-carboxamid (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-Dichlorphenyl)-4,5-dihydro-5-(trifluormethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamid, 4-[5-(3,5-Dichlorphenyl)-4,5-dihydro-5-(trifluormethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamid and 4-[(5S)-5-(3,5-Dichlorphenyl)-4,5-dihydro-5-(trifluormethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamid (known from WO 2013/050317 A1) (CAS 1332628-83-7), N-[3-Chlor-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluorpropyl)sulfinyl]propanamid, (+)-N-[3-Chlor-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluorpropyl)sulfinyl]propanamid and (−)-N-[3-Chlor-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluorpropyl)sulfinyl]propanamid (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 A1) (CAS 1477923-37-7), 5-[[(2E)-3-Chlor-2-propen-1-yl]amino]-1-[2,6-dichlor-4-(trifluormethyl)phenyl]-4-[(trifluormethyl)sulfinyl]-1H-pyrazol-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-Brom-N-[4-chlor-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chlor-2-pyridinyl)-1H-pyrazol-5-carboxamid, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); N-[4-Chlor-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chlor-2-pyridinyl)-3-(fluormethoxy)-1H-pyrazol-5-carboxamid (known from WO 2012/034403 A1) (CAS 1268277-22-0), N-[2-(5-Amino-1,3,4-thiadiazol-2-yl)-4-chlor-6-methylphenyl]-3-brom-1-(3-chlor-2-pyridinyl)-1H-pyrazol-5-carboxamid (known from WO 2011/085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-Dichlor-4-[(3,3-dichlor-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluormethyl)pyrimidin (known from CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-Cyanophenyl)-1-[3-(trifluormethyl)phenyl]ethyliden]-N-[4-(difluormethoxy)phenyl]hydrazincarboxamid (known from CN 101715774 A) (CAS 1232543-85-9); Cyclopropancarbonsaure-3-(2,2-dichlorethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenylester (known from CN 103524422 A) (CAS 1542271-46-4); (4aS)-7-Chlor-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluormethyl)thio]phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazin-4a(3H)-carbonsauremethylester (known from CN 102391261 A) (CAS 1370358-69-2); 6-Desoxy-3-O-ethyl-2,4-di-O-methyl-1-[N-[4-[1-[4-(1,1,2,2,2-pentafluorethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamat]-α-L-mannopyranose (known from US 2014/0275503 A1) (CAS 1181213-14-8); 8-(2-Cyclopropylmethoxy-4-trifluormethylphenoxy)-3-(6-trifluormethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octan (CAS 1253850-56-4), (8-anti)-8-(2-Cyclopropylmethoxy-4-trifluormethylphenoxy)-3-(6-trifluormethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octan (CAS 933798-27-7), (8-syn)-8-(2-Cyclopropylmethoxy-4-trifluormethylphenoxy)-3-(6-trifluormethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octan (known from WO 2007040280 A1, WO 2007040282 A1) (CAS 934001-66-8), N-[3-Chlor-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluorpropyl)thio]-propanamid (known from WO 2015/058021 A1, WO 2015/058028 A1) (CAS 1477919-27-9) and N-[4-(Aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-carboxamid (known from CN 103265527 A) (CAS 1452877-50-7), 5-(1,3-Dioxan-2-yl)-4-[[4-(trifluormethyl)phenyl]methoxy]-pyrimidin (known from WO 2013/115391 A1) (CAS 1449021-97-9), 3-(4-Chlor-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dion (known from WO 2014/187846 A1) (CAS 1638765-58-8), 3-(4-Chlor-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carbonsaureethylester (known from WO 2010/066780 A1, WO 2011151146 A1) (CAS 1229023-00-0), 4-[(5S)-5-(3,5-Dichlor-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(4R)-2-ethyl-3-oxo-4-isoxazolidinyl]-2-methyl-benzamid (known from WO 2011/067272, WO2013/050302) (CAS 1309959-62-3).

Examples of herbicides a) according to the invention are:

    • Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammoniumsulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bixlozone, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluormethyl)phenyl}piperidin-2-on, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-(methylsulfonyl)benzoyl}-1,3-dimethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazol-4-carboxylat, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, 2-[2-chloro-4-(methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-1-on, 4-{2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluorethoxy)methyl]benzoyl}-1-ethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazol-4-carboxylat, chlorophthalim, chlorotoluron, chlorthal-dimethyl, 3-[5-chloro-4-(trifluormethyl)pyridine-2-yl]-4-hydroxy-1-methylimidazolidine-2-on, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, -isooctyl, -potassium, and -sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, 3-(2,6-dimethylphenyl)-6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1-methylchinazolin-2,4(1H,3H)-dion, 1,3-dimethyl-4-[2-(methylsulfonyl)-4-(trifluormethyl)benzoyl]-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazol-4-carboxylat, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DMPA, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, ethyl-[(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetat, F-9960, F-5231, i.e. N-{2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-1H-tetrazol-1-yl]phenyl}ethanesulfonamide, F-7967, i. e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, fluro-chloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium, and -trimesium, H-9201, i.e. 0-(2,4-dimethyl-6-nitrophenyl)O-ethyl isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e. 1-(dimethoxyphosphoryl) ethyl-(2,4-dichlorophenoxy)acetate, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluormethyl)pyridine-2-yl]imidazolidine-2-on, 4-hydroxy-1-methyl-3-[4-(trifluormethyl)pyridine-2-yl]imidazolidine-2-on, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxido-2,3-dihydro-1-benzothiophen-5-yl)methanon, 6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1,5-dimethyl-3-(2-methylphenyl)chinazolin-2,4(1H,3H)-dion, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole, keto-spiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium, and -sodium, MCPB, MCPB-methyl, -ethy,l and -sodium, mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl, and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, 2-({2-[(2-methoxyethoxy)methyl]-6-(trifluormethyl)pyridin-3-yl}carbonyl)cyclohexan-1,3-dion, methyl isothiocyanate, 1-methyl-4-50 [(3,3,4-trimethyl-1,1-dioxido-2,3-dihydro-1-benzothiophen-5-yl)carbonyl]-1H-pyrazol-5-ylpropan-1-sulfonat, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e. N-(3-chloro-4-isopropylphenyl)-2-methylpentan amide, NGGC-011, napropamide, NC-310, i.e. [5-(benzyloxy)-1-methyl-1H-pyrazol-4-yl](2,4-dichlorophenyl)-methanone, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxy-carbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimi-sulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quino-clamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, QYM-201, QYR-301, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, tetflupyrolimet, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, ZJ-0862, i.e. 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline.

The at least one active ingredient is preferably selected from the group comprising fungicides selected from the group comprising classes as described here above (1) Inhibitors of the respiratory chain at complex, in particular azoles, (2) Inhibitors of the respiratory chain at complex I or II, (3) Inhibitors of the respiratory chain at complex, (4) Inhibitors of the mitosis and cell division, (6) Compounds capable to induce a host defence, (10) Inhibitors of the lipid and membrane synthesis, and (15).

Further preferred, the at least one active ingredient a) as fungicide is selected from the group comprising Trifloxystrobin, Bixafen, Prothioconazole, Inpyrfluxam, Isoflucypram, Fluopicolide, Fluopyram, Fluoxapiprolin.

The at least one insecticide is preferably selected from the group comprising insecticides selected from the group comprising classes as described here above (2 GABA-gated chloride channel antagonists, (3) Sodium channel modulators/voltage-dependent sodium channel blockers (4) (4) Nicotinic acetylcholine receptor (nAChR) competitive activators, (23) Inhibitors of acetyl-CoA carboxylase, (28) Ryanodinreceptor-modulators, (30) other active ingredients.

Also further preferred, the at least one active ingredient a) as insecticide is selected from the group comprising Spirotetramat, Tetraniliprole, Ethiprole, Imidacloprid, Deltamethrin, Flupyradifuron.

Lastly further preferred, the at least one active ingredient a) as herbicide is selected from the group comprising Triafamone, Tembotrione, Thiencarbazone-methyl, preferably in combination with safeners Isoxadifen-ethyl and Cyprosulfamat.

Even more preferred, the at least one active ingredient is selected from the group comprising trifloxystrobin, bixafen, prothioconazole, inpyrfluxam, isoflucypram, fluopicolide, fluopyram, fluoxapiprolin, spirotetramat, tetraniliprole, ethiprole, imidacloprid, deltamethrin, flupyradifuron, triafamone, tembotrione, thiencarbazone-methyl, isoxadifen-ethyl and cyprosulfamat.

All named active ingredients as described here above can be present in the form of the free compound or, if their functional groups enable this, an agrochemically active salt thereof.

Furthermore, mesomeric forms as well as stereoisomeres or enantiomeres, where applicable, shall be enclosed, as these modifications are well known to the skilled artisan, as well as polymorphic modifications.

If not otherwise specified, in the present invention solid, agrochemical active compounds a) are to be understood as meaning all substances customary for plant treatment, whose melting point is above 20° C.

Drift reducing agents b) Suitable drift reducing agents are poly(ethylene oxides), wherein the polymer has an average molecular weight preferably from 0.5 to 12 million g/mol, more preferred from 0.75 to 10 million g/mol, and most preferred from 1 to 8 million g/mol, and hydroxypropyl guar, as well as vegetable oils and vegetable oil esters and diesters (including esters with glycerine and propylene glycol).

Particularly preferred are methyl, ethyl, isopropyl, isobutyl, butyl, hexyl and ethylheyxl esters.

More preferred the vegetable oils and esters are selected from the group consisting of methyl oleate, methyl palmitate, rape seed oil methyl ester, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, ethylhexyl oleate, mixture of ethylhexyl myristate/laurate, ethylhexyl laurate, mixture of ethylhexyl caprylate/caprate, diisopropyl adipate, coconut oil propylene glycol diester, sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil, peanut oil, mixed caprylic and capric triglycerides, and mixed decanoyl and octanoyl glycerides.

Also suitable as drift reducing agent are mineral oils.

Uptake Enhancers (d)

The uptake enhancer may also be selected from the following group of compounds:

Other suitable uptake enhancers are alcohol ethoxylates, preferably selected from the group comprising ethoxylated alcohols, propoxy-ethoxylated alcohols, ethoxylated carboxylic acids, propoxy-ethoxylated carboxylic acids, or ethoxylated mono-, di- or triesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 5-40 EO units. Said ethoxylated or propoxy-ethoxylated alcohols or carboxylic acids are optionally further modified by addition of a methyl radical to the remaining alcohol functionality (cf. “Me end-capped”). The term “alcohols” according to d) refers to alcohols that can be branched or linear, saturated or unsaturated, with 6-22 carbon atoms and optionally carry additional substituents, such as OH groups. The term “carboxylic acids” according to d) refers to carboxylic acids that can be branched or linear, saturated or unsaturated, with 6-22 carbon atoms and optionally carry additional substituents, such as OH groups.

Suitable components according to d) by way of example are:

    • ethoxylated linear and/or branched fatty alcohols (e.g. Genapol® X-type of Clariant) with 2-20 EO units;
    • methyl end-capped, ethoxylated linear and/or branched fatty alcohols (e.g. Genapol® XM-type of Clariant) comprising 2-20 EO units;
    • ethoxylated coconut alcohols (e.g. Genapol® C-types of Clariant) comprising 2-20 EO units;
    • ethoxylated C12/15 alcohols (e.g. Synperonic® A-types of Croda) comprising 2-20 EO units;
    • propoxy-ethoxylated alcohols, branched or linear, e.g. Antarox® B/848 of Solvay, Atlas® G5000 of Croda, Lucramul® HOT 5902 of Levaco;
    • propoxy-ethoxylated fatty acids, Me end-capped, e.g. Leofat® OC0503M of Lion;
    • alkyl ether citrate surfactants (e.g. Adsee CE range, Akzo Nobel);
    • alkylpolysaccharides (e.g. Agnique® PG8107, PG8105 of BASF; Atplus® 438, AL-2559, AL-2575 of Croda);
    • ethoxylated mono- or diesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 10-40 EO units (e.g. Crovol® product range of Croda);
    • castor oil ethoxylates comprising an average of 5-40 EO units (e.g. Berol® range of Nouryon, Emulsogen® EL range of Clariant);
    • ethoxylated oleic acid (e.g. Alkamuls® A and AP) comprising 2-20 EO units;
    • ethoxylated sorbitan fatty acid esters comprising fatty acids with 8-18 carbon atoms and an average of 10-50 EO units (e.g. Arlatone® T, Tween range).

Rain-fast additives (e): Suitable rain-fast additives are acrylic based emulsion polymers or polymer dispersions and styrene based emulsion polymers or polymer dispersions d) are aqueous polymer dispersions with a Tg in the range from −100° C. to 30° C., preferably between −60° C. and 20° C., more preferably between −50° C. and 10° C., most preferably between −45° C. and 5° C., for example Acronal V215, Acronal 3612, Licomer ADH 205 and Atplus FA. Particularly preferred are Licomer ADH205, and Atplus FA.

Preferably, the polymer is selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and derivatives thereof, polyolefins, polyurethanes and natural polymers and derivatives thereof.

More preferably, the polymer is selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolysed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymer, polyurethane, cellulose, gelatine, caesin, oxidised starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose.

Most preferably the polymer is selected from copolymers of an acrylate and a styrene, wherein. Said acrylate selected from the list comprising 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof. Said styrene selected from the list comprising styrene, tert-butyl styrene, para-methyl styrene, or combinations thereof.

In a preferred embodiment the polymer, as described above, has a molecular weight of no more than 40000, preferably no more than 10000.

In a preferred embodiment the polymer D is an emulsion polymer as described in WO 2017/202684.

The glass transition temperature (Tg) is known for many polymers and is determined in the present invention, if not definded otherwise, according to ASTM E1356-08 (2014) “Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry” wherein the sample is dried prior to DSC at 110° C. for one hour to eliminate effect of water and/or solvent, DSC sample size of 10-15 mg, measured from −100° C. to 100° C. at 20° C./min under N2, with Tg defined as midpoint of the transition region.

Other Formulants (f):

f1 Suitable non-ionic surfactants or dispersing aids f1) are all substances of this type which can customarily be employed in agrochemical agents. Preferably, polyethylene oxide-polypropylene oxide block copolymers, preferably having a molecular weight of more than 6,000 g/mol or a polyethylene oxide content of more than 45%, more preferably having a molecular weight of more than 6,000 g/mol and a polyethylene oxide content of more than 45%, polyoxyalkylenamine derivatives, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters. Out of the examples mentioned above selected classes can be optionally phosphated, sulphonated or sulphated and neutralized with bases.

Possible anionic surfactants f1) are all substances of this type which can customarily be employed in agrochemical agents. Alkali metal, alkaline earth metal and ammonium salts of alkylsulphonic or alkylphospohric acids as well as alkylarylsulphonic or alkylarylphosphoric acids are preferred. A further preferred group of anionic surfactants or dispersing aids are alkali metal, alkaline earth metal and ammonium salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of alkylnaphthalene sulphonic acids, salts of naphthalene-sulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.

f2 A rheological modifier is an additive that when added to the recipe at a concentration that reduces the gravitational separation of the dispersed active ingredient during storage results in a substantial increase in the viscosity at low shear rates. Low shear rates are defined as 0.1 s−1 and below and a substantial increase as greater than ×2 for the purpose of this invention. The viscosity can be measured by a rotational shear rheometer.

Suitable rheological modifiers E2) by way of example are:

    • Polysaccharides including xanthan gum, and hydroxyethyl cellulose. Examples are Kelzan®, Rhodopol® G and 23, Satiaxane® CX911 and Natrosol® 250 range.
    • Clays including montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite. Examples are Veegum® R, Van Gel® B, Bentone® 34, 38, CT, HC, EW, Pangel® M100, M200, M300, S, M, W, Attagel® 50, Laponite® RD,
    • Fumed and precipitated silica, examples are Aerosil® 200, Sipernat® 22.

Preferred are xanthan gum, montmorillonite clays, bentonite clays and fumed silica.

f3 Suitable antifoam substances e3) are all substances which can customarily be employed in agrochemical agents for this purpose. Silicone oils, silicone oil preparations are preferred. Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAF-184® fron Silchem, Foam-Clear ArraPro-S® from Basildon Chemical Company Ltd, SAG® 1572 and SAG® 30 from Momentive [Dimethyl siloxanes and silicones, CAS No. 63148-62-9]. Preferred is SAG® 1572.

f4 Suitable antifreeze agents are all substances which can customarily be employed in agrochemical agents for this purpose. Suitable examples are propylene glycol, ethylene glycol, urea and glycerine.

f5 Suitable other formulants e5) are selected from biocides, colourants, pH adjusters, buffers, stabilisers, antioxidants, inert filling materials, humectants, crystal growth inhibitors, micronutirients by way of example are:

    • Possible preservatives are all substances which can customarily be employed in agrochemical agents for this purpose. Suitable examples for preservatives are preparations containing 5-chloro-2-methyl-4-isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1,2-benzisothiazol-3(2H)-one [CAS-No. 2634-33-5]. Examples which may be mentioned are Preventol® D7 (Lanxess), Kathon® CG/ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).
    • Possible colourants are all substances which can customarily be employed in agrochemical agents for this purpose. Titanium dioxide, carbon black, zinc oxide, blue pigments, Brilliant Blue FCF, red pigments and Permanent Red FGR may be mentioned by way of example.
    • Possible pH adjusters and buffers are all substances which can customarily be employed in agrochemical agents for this purpose. Citric acid, sulfuric acid, hydrochloric acid, sodium hydroxide, sodium hydrogen phosphate (Na2HPO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), potassium hydrogen phosphate (K2HPO4), may be mentioned by way of example.

Suitable stabilisers and antioxidants are all substances which can customarily be employed in agrochemical agents for this purpose. Butylhydroxytoluene [3,5-Di-tert-butyl-4-hydroxytoluol, CAS-No. 128-37-0] is preferred.

Carriers (g) are those which can customarily be used for this purpose in agrochemical formulations.

A carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert, and which may be used as a solvent. The carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, in particular ammonium sulfates, ammonium phosphates and ammonium nitrates, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel and synthetic rock flours, such as finely divided silica, alumina and silicates. Examples of typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks.

Preferred solid carriers are selected from clays, talc and silica.

Examples of suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof. Examples of suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of

    • alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as ethanol, propanol, butanol, benzylalcohol, cyclohexanol or glycol, 2-ethyl hexanol),
    • ethers such as dioctyl ether, tetrahydrofuran, dimethyl isosorbide, solketal, cyclopentyl methyl ether, solvents offered by Dow under the Dowanol Product Range e.g. Dowanol DPM, anisole, phenetole, different molecular weight grades of dimethyl polyethylene glycol, different molecular weight grades of dimethyl polypropylene glycol, dibenzyl ether
    • ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone, propiophenone),
    • lactate esters, such as methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethyl hexyl lactate
    • (poly)ethers such as different molecular weight grades of polyethylene glycol, different molecular weight grades of polypropylene glycol
    • unsubstituted and substituted amines
    • amides (such as dimethylformamide, or N,N-dimethyl lactamide, or N-formyl morpholine, or fatty acid amides such N,N-dimethyl decanamide or N,N-dimethyl dec-9-en-amide) and esters thereof
    • lactams (such as 2-pyrrolidone, or N-alkylpyrrolidones, such as N-methylpyrrolidone, or N-butylpyrrolidone, or N-octylpyrrolidone, or N-dodecylpyrrolidone or N-methyl caprolactam, N-alkyl caprolactam)
    • lactones (such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, or alpha-methyl gamma-butyrolactone
    • sulfones and sulfoxides (such as dimethyl sulfoxide),
    • nitriles, such as linear or cyclic alkyl nitriles, in particular acetonitrile, cyclohexane carbonitrile, octanonitrile, dodecanonitrile).
    • linear and cyclic carbonates, such as diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate, or ethylene carbonate, propylene carbonate, butylene carbonate, glycerine carbonate

Most preferred the carrier is water.

These spray liquids are applied by customary methods, i.e., for example, by spraying, pouring or injecting, in particular by spraying, and most particular by spraying by UAV.

The application rate of the formulations according to the invention can be varied within a relatively wide range. It is guided by the particular active agrochemicals and by their amount in the formulations.

With the aid of the formulations according to the invention it is possible to deliver active agrochemical to plants and/or their habitat in a particularly advantageous way.

The present invention is also directed to the use of agrochemical compositions according to the invention for the application of the agrochemical active compounds contained to plants and/or their habitat.

With the formulations of the invention it is possible to treat all plants and plant parts. By plants here are meant all plants and plant populations, such as desirable and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and gene-technological methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by varietal property rights. By plant parts are to be meant all above-ground and below-ground parts and organs of the plants, such as shoot, leaf, flower and root, an exemplary listing embracing leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. The plant parts also include harvested material and also vegetative and generative propagation material.

What may be emphasized in this context is the particularly advantageous effect of the formulations according to the invention with regard to their use in cereal plants such as, for example, wheat, oats, barley, spelt, triticale and rye, but also in maize, sorghum and millet, rice, sugar cane, soya beans, sunflowers, potatoes, cotton, oilseed rape, canola, tobacco, sugar beet, fodder beet, asparagus, hops and fruit plants (comprising pome fruit such as, for example, apples and pears, stone fruit such as, for example, peaches, nectarines, cherries, plums and apricots, citrus fruits such as, for example, oranges, grapefruits, limes, lemons, kumquats, tangerines and satsumas, nuts such as, for example, pistachios, almonds, walnuts and pecan nuts, tropical fruits such as, for example, mango, papaya, pineapple, dates and bananas, and grapes) and vegetables (comprising leaf vegetables such as, for example, endives, corn salad, Florence fennel, lettuce, cos lettuce, Swiss chard, spinach and chicory for salad use, cabbages such as, for example, cauliflower, broccoli, Chinese leaves, Brassica oleracea (L.) convar. acephala var. sabellica L. (curly kale, feathered cabbage), kohlrabi, Brussels sprouts, red cabbage, white cabbage and Savoy cabbage, fruit vegetables such as, for example, aubergines, cucumbers, capsicums, table pumpkins, tomatoes, courgettes and sweetcorn, root vegetables such as, for example celeriac, wild turnips, carrots, including yellow cultivars, Raphanus sativus var. niger and var. radicula, beetroot, scorzonera and celery, legumes such as, for example, peas and beans, and vegetables from the Allium family such as, for example, leeks and onions.

The treatment of the plants and plant parts in accordance with the invention with the inventive formulations is carried out directly or by action on their environment, habitat or storage area in accordance with the customary treatment methods, for example by dipping, spraying, vaporizing, atomizing, broadcasting or painting on and, in the case of propagation material, especially seeds, additionally by single or multiple coating.

The active agrochemicals comprised develop a better biological activity than when applied in the form of the corresponding conventional formulations.

If not otherwise defined in this application, the molecular weight refers to the weight-average molecular weight Mw which is determined by GPC in methylene chloride at 25° C. with polystyrene as the standard.

Leaf Surfaces

In Tables M1a and M1b the contact angle of water on leaf surfaces for textured and non-textured is shown.

TABLE M1a Plants with textured leaves Contact angle of water ° Plant Species (adaxial) barley Hordeum vulgare 143° (var. Montoya) corn, BBCH-11 Zea mays 150° corn, BBCH-12 Zea mays 149° corn, BBCH-13/14 Zea mays 148° soybean, BBCH-12 Glycine max 149° soybean, BBCH-13 Glycine max 144° rice Oryza sativa 180° wheat, BBCH-12 Triticum aestivum 148° fat-hen Chenopodium album 137° purple crabgrass Digitaria sanguinalis 144°

TABLE M1b Plants with non-textured leaves Contact angle of water ° Plant Species (adaxial) apple Malus domestica 104° tomato Solanum lycopersicum 106° corn, BBCH-15/16 Zea mays 108° corn, BBCH-17 Zea mays 107° corn, BBCH-18 Zea mays  96° corn, BBCH-19 Zea mays  87° velvetleaf Abutilon theophrasti 103° redroot pigweed Amaranthus retroflexus not measured

Examples of non-textured crops and plants include tomatoes, peppers, potatoes, carrot, celery, sugar beet, beetroot, spinach, lettuce, beans, peas, clover, apple, pear, peach, apricot, plum, mango, avocado, olive, citrus, orange, lemon, lime, grape, fig, cucumber, melon, water melon, strawberry, raspberry, blueberry, sunflower, pumpkin, soybean (≥GS 16 (BBCH 16)), corn (≥GS 15 (BBCH 15), cotton.

Examples of textured crops and plants include garlic, onions, leeks, soybean (≤GS 16 (BBCH 16)), oats, wheat, barley, rice, sugarcane, pineapple, banana, linseed, lilies, orchids, corn (≤GS 15 (BBCH 15)), cabbage, brussels sprouts, broccoli, cauliflower, rye, rapeseed, tulips and peanut.

Examples of non-textured weeds include Abutilon theophrasti, Capsella bursa-pastoris, Datura stramonium, Galium aparine, Ipomoea purpurea, Polygonum lapathifolium, Portulaca oleracea, Senecio vulgaris, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Xanthium orientale, Cyperus rotundus, and Amaranthus retroflexus.

Examples of textured weeds include Cassia obtusifolia, Chenopodium album, Agropyron repens, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Brachiaria plantaginea, Bromus secalinus, Cynodon dactylon, Digitaria sanguinalis, Echinochloa crus-galli, Panicum dichotomiflorum, Poa annua, Setaria faberi and Sorghum halepense.

The invention is illustrated by the following examples.

EXAMPLES

Method 1: Flowables SC and SE Preparation (Oil)

The method of the preparation of flowable suspension concentrate and suspo-emulsion formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan (f) in water and the biocides (f) was prepared with low shear stirring. If present in the recipe, a 50% oil in water emulsion of oil (b) was prepared by adding oil (50%) to water (49%) and Synperonic PE/F127 (1%) in solution (or equivalent surfactant) under high shear mixing (Ultra-Turrax®). The active ingredient (a), non-ionic and anionic dispersants (f), antifoam (f) and other formulants (f) were mixed with the water to form a slurry, first mixed with a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills (Eiger® 250 Mini Motormill) to achieve a particles size D(v,0.9) typically 1 to 15 microns. Then the additives (b) as the 50% emulsion prepared above, (d), (e) and xanthan gel prepared above were added and mixed in with low shear stirring until homogeneous. Finally, the pH is adjusted if needed with acid or base (f).

Flowable formulations containing small levels of emulsified oils can be described as both Suspension Concentrate and Suspo-emulsion formulation types (www.croplife.org, Technical Monograph No: 2, Catalogue of pesticide formulation types and international coding system, Edition: March 2017).

Method 2: Flowables SC Preparation (Polymer)

The method of the preparation of flowable suspension concentrate formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan (f) in water and the biocides (f) was prepared with low shear stirring. If present in the recipe, a 1-4% of polymer (b) was prepared. The active ingredient (a), non-ionic and anionic dispersants (f), antifoam (f) and other formulants (f) were mixed with the water to form a slurry, first mixed with a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills (Eiger® 250 Mini Motormill) to achieve a particles size D(v,0.9) typically 1 to 15 microns. Then the additives (b) as the polymer solution prepared above, (d), (e) and xanthan gel prepared above were added and mixed in with low shear stirring until homogeneous. Finally, the pH is adjusted if needed with acid or base (f).

The polymer (b) solution is prepared according to the viscosity concentration limit and content required in the recipe. Typical values are: Polyox WSR301 (1-2%), Polyox WSR N60K (1-3%), Polyox WSR N12K (2-4%), AgRho DS2000 (1-2%).

Method 3: EC Preparation

The method of the preparation of EC formulations are known in the art and can be produced by known methods familiar to those skilled in the art. In general, EC formulations are obtained by mixing the active ingredients in a vessel equipped with a stirring device. In some cases the dissolving or mixing was facilitated by raising the temperature slightly (not exceeding 60° C.). Stirring is continued until a homogeneous mixture has been obtained.

Method 4: OD Preparation

Formulation components are weighed in, homogenized with a high-shear device (e.g. Ultraturrax or colloidal mill) and subsequently milled in a bead mill (e.g. Dispermat SL50, 80% filling, 1.0-1.25 mm glass beads, 4000 rpm, circulation grinding) until a particle size of <10μ is achieved. Alternatively, formulation components are mixed in a bottle followed by addition of approx. 25 vol.-% of 1.0-1.25 mm glass beads. The bottle is then closed, clamped in an agitator apparatus (e.g. Retsch MM301) and treated at 30 Hz for several minutes until a particle size of <10p is achieved.

Method 5: WG Preparation

The methods of the preparation water dispersible granule formulations are known in the art and can be produced by known methods familiar to those skilled in the art.

For example, to produce a fluid bed granule first a water-based technical concentrate has to be prepared. With low shear stirring all ingredients (a, b and c) like e.g. the active ingredient, surfactants, dispersants, binder, antifoam, anti-drift-agent, and filler are mixed in water and finally pre-milled in a high shear rotor-stator mixer (Ultra-Turrax®) to reduce the particle size D(v,0.9) to approximately 50 microns, afterwards passed through one or more bead mills (KDL, Bachofen, Dynomill, Bdhler, Drais, Lehmann) to achieve a particles size D(v,0.9) typically 1 to 15 microns. This water-based technical concentrate is then spray-dried in a fluid-bed granulation process to form the wettable granules (WG).

The particle size is determined according to CIPAC (CIPAC=Collaborative International Pesticides Analytical Council; www.cipac.org) method MT 187. The particle size distribution is determined by means of laser diffraction. A representative amount of sample is dispersed in degassed water at ambient temperature (self-saturation of the sample), treated with ultrasound (usually 60 s) and then measured in a device from the Malvern Mastersizer series (Malvern Panalytical). The scattered light is measured at various angles using a multi-element detector and the associated numerical values are recorded. With the help of the Fraunhofer model, the proportion of certain size classes is calculated from the scatter data and from this a volume-weighted particle size distribution is calculated. Usually the d50 or d90 value=active ingredient particle size (50 or 90% of all volume particles) is given. The average particle size denotes the d50 value.

Likewise, any other spraying process, like e.g. classical spray drying can be used as granulation method.

A further technique to produce water dispersible granules is for example low pressure extrusion. The ingredients of the formulation are mixed in dry from and are subsequently milled, e.g. using air-jet milling to reduce the particle size. Subsequently this dry powder is stirred while water is added to the mixture (approximately 10-30 wt %, dependent on the composition of the formulation). In a further step the mixture is pushed through an extruder (like a dome extruder, double dome extruder, basket extruder, sieve mill, or similar device) with a die size of usually between 0.8 and 1.2 mm to form the extrudates. In a last step the extrudates are post-dried, e.g. in a fluidized bed dryer to reduce the water content of the powder, commonly to a level of 1-3 wt % of residual water.

Method 6: Drift Wind Chamber

A custom-built drift chamber approximately 2.8 m wide, 2.8 m long and 1 m in height containing a spray nozzle, a horizontal windflow, and a drift collector screen was used to measure the drift of formulations. The spray nozzle is at a height of 0.5 m above the base of the chamber and a distance of 1.4 m from the collector screen approximately 0.6 m in height across end wall of the spray chamber. The spray liquid collected by the detector screen is weighed and the amount of drift from the spray calculated from the flow rate of the spray liquid and the fraction captured by the detector screen. The velocity of the windflow was 3 m/s. The formulations were diluted in water to the required concentration, sprayed through a TeeJet® TP8002EVS nozzle at a pressure of 2 bar and the amount of drift recorded once a steady state was achieved. This technique provides a comparative measurement of drift between different recipes.

Method 7: Drift Droplet Size P15

The formulations were diluted in water to the required concentration, sprayed through a TeeJet® TP8002EVS nozzle at a pressure of 3 bar and the droplet size spectra measured with an Oxford Lasers VisiSize P15 which captures images of the spray droplets and measures their size. The spray nozzle was positioned 20 cm above the image capture point slowly moved repeatedly across the image capture window of the VisiSize P15 until 5000 to 10000 droplet images were captured. The droplet size spectra were calculated by the instrument software as volume % less than 100 microns and/or volume % less than 150 microns, which are commonly regarded as the driftable fraction of the spray droplets. The relative amount of driftable droplets was calculated as the % volume <100 microns for the invention recipe/% volume <100 microns for the reference recipe ×100(%) and/or as the % volume <150 microns for the invention recipe/% volume <150 microns for the reference recipe ×100(%). Accordingly, a value of 60% would demonstrate that the invention recipe has only 60% of the driftable fraction of spray droplets compared to the reference recipe which would have here 100%.

Method 8: Drift Droplet Size Laser

The formulations were diluted in water to the required concentration, sprayed through a TeeJet 11002VS nozzle at a pressure of 3 bar and the droplet size spectra measured with a Malvern SprayTec laser diffraction instrument with a single, long-axis scan across the spray fan at a distance of 350 mm below the nozzle.

Method 9: Drift Filter Paper Deposits

The formulations were diluted in water to the required concentration with a small amount of a fluorescent tracer (Tinopal SC), sprayed through a TeeJet 11002E nozzle at a pressure of 2 bar onto filter paper and the droplet size spectra measured using ImageJ.

The filter paper is photographed using a digital camera, with UV light [365 nm] as the illuminating resource. In the pictures of filter paper, droplet deposits which are fluorescently labelled have much higher intensity than the filter paper and other background.

Images are processed in the ImageJ software (www.fiji.com). First, the RGB image is split into Red, Green and Blue channel, only the Green or Blue channel is used for further analysis, depending on the intensity of the original image. Next, the ‘Subtract background’ algorithm is applied to the single channel image to remove background noise, which in turn improve the contrast between the droplet deposits and the background. Afterward, an intensity threshold is generated automatically and applied by the software, resulting in a binary image where droplet deposits are remained with maximum intensity while the background such as the filter paper itself has zero intensity. Finally, the ‘watershed’ algorithm is applied to the binary image, in order to segment droplets that are connected in the image. All remained and segmented objects are detected and labelled with their positions and sizes. The size of each object represents the area of each deposit, is in the unit of um2.

The nozzle used in the spray test has a VMD of 210 um with water. The Volume Median Diameter (VMD) is determined from the cumulative distribution functions (CDFs) of droplet volume V, droplets that have sizes smaller than VMD account for 50% of the total sprayed volume. Since there is no direct correlation between the deposit area obtained from filter paper and the actual droplet size/volume, the VMD of water has been used as a reference to rescale the CDFs of formulation sprays.

From ImageJ analysis, the area (A) of each droplet deposit on filter paper is recorded. The diameter of each deposit dA=(4A/π)1/2, the estimate droplet volume Vestimate=π·dA3/6. The CDF of the basic formulation is plotted using the estimate droplet volume Vestimate, which is calculated from the deposit area on the filter paper, VMD of the basic formulation is also obtained from the CDF curve. With the assumption that the basic formulation has similar droplet size distribution as water, by matching the VMD of the basic formulation to VMD of water, a size factor f=VMDbasic/VMDwater is generated. Given a droplet deposit area A from the filter paper, the actual droplet diameter d=f·(4A/π)1/2, the droplet volume V=π·d3/6.

The cumulative distributions of droplet volume V of different formulations are plotted with bins of logarithmic scale. From each cumulative distribution curve, the percentage of droplets that have diameters less than 150 um is counted. This volume percentage of fine droplets corresponds to the degree of drift potential. Using the percentage of a basic formulation (pbasic) as a reference, the relative difference of the percentage between a formulation with adjuvants (p) and the basic formulation is computed. The relative difference r=p/pbasic·100%. If the relative difference (r) is lower than 100%, the formulation has lower potential for drift compared with a basic formulation, and vice versa.

Method 10: Insecticide Greenhouse Tests

Selected crops were grown under greenhouse conditions in plastic pots containing “peat soil T”. At appropriate crop stage, plants were prepared for the treatments, e.g. by infestation with target pest approximately 2 days prior to treatment (s. table below).

Spray solutions were prepared with different doses of active ingredient directly by dilution of formulations with tap water and addition of appropriate amount of additives in tank mix, where required.

The application was conducted with a tracksprayer onto the upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

After treatment, plants were artificially infested, if needed, and kept during test duration in a greenhouse or climate chamber. The efficacy of the treatments was rated after evaluation of mortality (in general, given in %) and/or plant protection (calculated e.g. from feeding damage in comparison to corresponding controls) at different points of time. Only mean values are reported.

TABLE M3 Pests and crops used in the tests. crop crop stage infestation pest English name pest life stage test objective soybean BBCH12, after Nezara green stink bug 10× nymphs N2- contact and oral 5 plants treatment viridula N3 uptake in pot cabbage BBCH12, prior to Myzus green peach mixed translaminar 1-leaf treatment persicae aphid population activity

Selected crops were grown under greenhouse conditions in plastic pots containing “peat soil T”. At appropriate crop stage, plants were prepared for the treatments, e.g. by infestation with target pest approximately 2 days prior to treatment (table M3).

Spray solutions were prepared with different doses of active ingredient directly by dilution of formulations with tap water and addition of appropriate amount of additives in tank mix, where required.

The application was conducted with tracksprayer onto upperside of leaves with 300 l/ha or 10 l/ha application volume. Nozzles used: TeeJet TP8003E (for 300 l/ha) and Lechler's 652.246 together with a pulse-width-module (PWM) (for 10 l/ha). For each single dose applied, usually 2 to 5 replicates were simultaneously treated.

After treatment, plants were artificially infested, if needed, and kept during test duration in a greenhouse or climate chamber. The efficacy of the treatments was rated after evaluation of mortality (in general, given in %) and/or plant protection (calculated e.g. from feeding damage in comparison to corresponding controls) at different points of time. Only mean values are reported.

Method 11: Description for Herbicide Greenhouse Tests

Seeds of crops and monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants are treated at the one- to two-leaf stage. The test herbicide formulations are prepared with different concentrations and sprayed onto the surface of the green parts of the plants using different water application rates: 200 I/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications is TeeJet DG 95015 EVS. The ULV application rate is achieved by using a pulse-width-modulation (PWM) -system that gets attached to the nozzle and the track sprayer device. After application, the test plants were left to stand in the greenhouse for 3 to 4 weeks under optimum growth conditions. Then, the activity of the herbicide formulation is scored visually (for example: 100% activity=the whole plant material is dead, 0% activity=plants are similar to the non-treated control plants).

TABLE M4 Plant species used in the tests. Plant species Abbreviation/EPPO Code Crop Variety Setaria viridis SETVI Echinochloa crus-galli ECHCG Alopecurus myosuroides ALOMY Hordeum murinum HORMU Avena fatua AVEFA Lolium rigidum LOLRI Matricaria inodora MATIN Veronica persica VERPE Abutilon theophrasti ABUTH Pharbitis purpurea PHBPU Polygonum convolvulus POLCO Amaranthus retroflexus AMARE Stellaria media STEME Zea mays ZEAMA Aventura Triticum aestivum TRZAS Triso Brassica napus BRSNW Fontan

Method 12: Description for Fungicide Greenhouse Tests

Seeds were laid out in “peat soil T” in plastic pots, covered with soil and cultivated in a greenhouse under optimum growth conditions. Two to three weeks after sowing, the test plants were treated at the one- to two-leaf stage. The test fungicide formulations were prepared with different concentrations and sprayed onto the surface of the plants using different water application rates: 200 I/ha as a standard conventional rate and 10 l/ha as an ultra-low-volume (ULV) application rate. The nozzle type used for all applications was TeeJet TP 8002E, used with 2 bar and 500-600 mm height above plant level. Cereal plants were put in an 450 angle as this reflected best the spray conditions in the field for cereals. The ULV application rate was achieved by using a pulse-width-modulation (PWM) system attached to the nozzle and the track sprayer device at 30 Hz, opening 8%-100% (10l/ha-200 l/ha spray volume).

In a protective treatment the test plants were inoculated 1 day after the spray application with the respective disease and left to stand in the greenhouse for 1 to 2 weeks under optimum growth conditions. Then, the activity of the fungicide formulation was assessed visually.

In curative conditions plants were first inoculated with the disease and treated 1-3 days later with the fungicide formulations. Visual assessment of the disease was done 3-6 days after application of formulations (dat).

The practices for inoculation are well known to those skilled in the art.

TABLE M5 Diseases and crops used in the tests. Abbreviation/ Plant species Crop Variety Disease English Name EPPO Code disease Soybean Merlin Phakopsora Soybean rust PHAKPA pachyrhizi Wheat Monopol Puccinia recondita Brown rust PUCCRT Barley Gaulois Pyrenophora teres Net blotch PYRNTE Barley Villa Blumeria graminis Powdery mildew ERYSGH Tomato Rentita Phytophtora Late blight PHYTIN infestans

Method 13: Cuticle Penetration Test

The cuticle penetration test is a further developed and adapted version of the test method SOFU (simulation of foliar uptake) originally described by Schönherr and Baur (Schönherr, J., Baur, P. (1996), Effects of temperature, surfactants and other adjuvants on rates of uptake of organic compounds. In: The plant cuticle—an integrated functional approach, 134-155. Kerstiens, G. (ed.), BIOS Scientific publisher, Oxford); it is well suited for systematic and mechanistic studies on the effects of formulations, adjuvants and solvents on the penetration of agrochemicals.

Apple leaf cuticles were isolated from leaves taken from trees growing in an orchard as described by Schönherr and Riederer (Schönherr, J., Riederer, M. (1986), Plant cuticles sorb lipophilic compounds during enzymatic isolation. Plant Cell Environ. 9, 459-466). Only the astomatous cuticular membranes of the upper leaf surface lacking stomatal pores were obtained. Discs having diameters of 18 mm were punched out of the leaves and infiltrated with an enzymatic solution of pectinase and cellulase. The cuticular membranes were separated from the digested leaf cell broth, cleaned by gently washing with water and dried. After storage for about four weeks the permeability of the cuticles reaches a constant level and the cuticular membranes are ready for the use in the penetration test.

The cuticular membranes were applied to diffusion vessels. The correct orientation is important: the inner surface of the cuticle should face to the inner side of the diffusion vessel. A spray was applied in a spray chamber to the outer surface of the cuticle. The diffusion vessel was turned around and carefully filled with acceptor solution. Aqueous mixture buffered to pH 5.5 was used as acceptor medium to simulate the apoplast as natural desorption medium at the inner surface of the cuticle.

The diffusion vessels filled with acceptor and stirrer were transferred to a temperature-controlled stainless steel block which ensures not only a well-defined temperature but also a constant humidity at the cuticle surface with the spray deposit. The temperature at the beginning of experiments was 25° C., 30° C. or 35° C. and kept constant or changed to 35° C. 24 h after application at constantly 60% relative humidity.

An autosampler took aliquots of the acceptor in regular intervals and the content of active ingredient is determined by HPLC (DAD or MS). All data points were finally processed to obtain a penetration kinetic. As the variation in the penetration barrier of the cuticles is high, five to ten repetitions of each penetration kinetic were made.

Method 14: Cuticle Wash-Off

A disc from an apple cuticle was fixed with the outside surface facing upwards to a glass microscope slide with a thin layer of medium viscosity silicone oil. To this 0.9 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water were applied with a micropipette and left to dry for 1 hour. Each deposit was examined in an optical transmission microscope fitted with crossed polarising filters and an image recorded. The slide containing the cuticle with the dried droplets of the formulations was held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The glass slide was allowed to dry and the deposits were re-examined in the microscope and compared to the original images. The amount of active ingredient washed off was visually estimated and recorded in steps of 10%. Three replicates were measured and the mean value recorded.

Method 15: Leaf Wash-Off

Apple or corn leaf sections were attached to a glass microscope slide. To this 0.9 to 1.4 μl drops of the different formulations diluted at the spray dilution in deionised water containing 5% CIPAC C water and a small amount of fluorescent tracer (Tinopal OB as a micron sized aqueous suspension) were applied with a micropipette and left to dry for 1 hour. Under UV illumination (365 nm) the leaf deposits were imaged by a digital camera. The leaf sections were then held under gently running deionised water (flow rate approximately 300 ml/minute at a height 10 cm below the tap outlet) for 15 s. The leaf sections were allowed to dry and the deposits were re-imaged and compared to the original images. The amount of active ingredient washed off was visually estimated between 5 with most remaining and 1 with most removed. Three or more replicates were measured and the mean value recorded.

Method 16: Coverage (Spray)

Greenhouse plants in the development stage as indicated in Tables M1a & M1b were used for these experiments. Single leaves were cut just before the spraying experiment, placed into petri dishes and attached by tape at both tips at 0° (horizontally) or at 600 (so that 50% of leaf area can be sprayed).

The leaves were carried with caution to avoid damage of the wax surface. These horizontally orientated leaves were either a) placed into a spay chamber where the spray liquid was applied via a hydraulic nozzle.

A small amount of UV dye was added to the spray liquid to visualize the spray deposits under UV light. The concentration of the dye has been chosen such that it does not influence the surface properties of the spray liquid and does not contribute to spreading itself. Tinopal OB as a colloidal suspension was used for all flowable and solid formulation such as WG, SC, OD and SE. Tinopal CBS-X or Blankophor SOL were used for formulations where active ingredient is dissolved such as EC, EW and SL. The Tinopal CBS-X was dissolved in the aqueous phase and the Blankophor SOL dissolved in the oil phase.

After evaporation of the spray liquid, the leaves were placed into a Camag, Reprostar 3 UV chamber where pictures of spray deposits were taken under visual light and under UV light at 366 nm. A Canon EOS 700D digital camera was attached to the UV chamber and used to acquire images the leaves. Pictures taken under visual light were used to subtract the leaf shape from the background. ImageJ software was used to calculate either a) the percentage coverage of the applied spray for sprayed leaves or b) spread area for pipetted drops in mm2.

Method 17: Coverage (Pipette)

Greenhouse plants in the development stage as indicated in Tables M1a & M1b were used for these experiments. A 1.4 μl drop of spray liquid containing a small amount of fluorescent tracer (Tinopal OB as a micron sized aqueous suspension) was pipetted on top without touching the leaf surface and left to dry. Under UV illumination (365 nm) the leaf deposits were imaged by a digital camera and the area of the deposits measured using ImageJ software (www.fiji.com).

Method 18: Persistent Foam

The persistent foam was determined according to CIPAC Method MT 47.1 with the conditions of using the recipe dose rate and spray volumes indicated in each example and the foam recorded after 1 minute and 3 minutes (www.cipac.org).

Materials

TABLE MAT1 Exemplified trade names and CAS-No's of preferred drift reducing materials-Polymers (b) Product Chemical name Cas No. Supplier Polyox ® WSR N12K Poly(ethylene oxide) 25322-68-3 Dupont (average molecular weight 1 million g/mol) Polyox ® WSR N60K Poly(ethylene oxide) 25322-68-3 Dupont (average molecular weight 2 million g/mol) Polyox ® WSR 301 Poly(ethylene oxide) 25322-68-3 Dupont (average molecular weight 4 million g/mol) Polyox ® WSR 308 Poly(ethylene oxide) 25322-68-3 Dupont (average molecular weight 8 million g/mol) AgRho ® DR2000 hydroxypropyl guar 68442-94-4. Solvay 39421-75-5 Jaguar ® HP-120 hydroxypropyl guar 68442-94-4. Solvay 39421-75-5 Jaguar ® HP-8 hydroxypropyl guar 68442-94-4. Solvay 39421-75-5 Jaguar ® 308 NB hydroxypropyl guar 68442-94-4. Solvay 39421-75-5

TABLE MAT2 Exemplified trade names and CAS-No's of preferred drift reducing materials-Oils (b) Product Chemical name Cas No. Supplier Radia ® 7060 methyl oleate 112-62-9 Oleon NV, BE Radia ® 7120 methyl palmitate 112-39-0 Oleon NV, BE AGNIQUE MER 18 RD-F, Rape seed oil methyl 67762-38-3. Clariant Edenor ® MESU ester 85586-25-0 BASF Crodamol ® EO ethyl oleate 111-62-6 Croda Estol ® 1514 iso-propyl myristate 110-27-0 Croda Crodamol ® IPM Radia ® 7732 iso-propyl palmitate 142-91-6 Oleon NV, BE Crodamol ® IPP Croda, UK Radia ® 7129 ethylhexyl palmitate 29806-73-3 Oleon NV, BE Crodamol ® OP Croda, UK Radia ® 7130 ethylhexyl oleate 26399-02-0 Oleon NV, BE Radia ® 7128 ethylhexyl 29806-75-5 Oleon NV, BE myristate/laurate C12/C14 Radia ® 7127 ethylhexyl laurate 20292-08-4 Oleon NV, BE Radia ® 7126 ethylhexyl 63321-70-0 Oleon NV, BE caprylate/caprate C8/10 Crodamol DA di-isopropyl adipate 6938-94-9 Croda Crodamol PC DAB Propyleneglycol di-ester 85409-09-2 Croda of coconut fatty acids Sunflower oil Triglycerides from 8001-21-6 different C14-C18 fatty acids, predominantly unsaturated Rapeseed oil Triglycerides from 8002-13-9 different C14-C18 fatty acids, predominantly unsaturated Corn oil Triglycerides from 8001-30-7 different C14-C18 fatty acids, predominantly unsaturated Soybean oil Triglycerides from 8001-22-7 different C14-C18 fatty acids, predominantly unsaturated Rice bran oil Triglycerides from 68553-81-1 different C14-C18 fatty acids, predominantly unsaturated Olive oil Peanut oil Radia ® 7104 Caprylic, capric 73398-61-5. Oleon NV, BE triglycerides, neutral 65381-09-1 vegetable oil Miglyol 812N Glycerides, mixed 73398-61-5. IOI Oleochemical decanoyl and octanoyl 65381-09-1

TABLE MAT4 Exemplified trade names and CAS-No's of preferred uptake enhancing compounds (d) Product Chemical name Cas No. Supplier Emulsogen ® Ethoxylated Castor Oil with 61791-12-6 Clariant EL 400 40 EO Etocas ® 10 Ethoxylated Castor Oil with 61791-12-6 Croda Crovol ® 10 EO fats and glyceridic oils, 70377-91-2 Croda CR70G vegetable, ethoxylated Synperonic ® alcohol ethoxylate 68131-39-5 Croda A3 (C12/C15-EO3) Synperonic ® alcohol ethoxylate 68131-39-5 Croda A7 (C12/C15-EO7) Genapol ® alcohol ethoxylate 9043-30-5 Clariant X060 (iso-C13-EO6) Alkamuls ® A Oleic acid, ethoxylated 9004-96-0 Solvay Lucramul ® alcohol ethoxylate- 64366-70-7 Levaco HOT 5902 propoxylate Antarox B/848 Butyl alcohol 9038-95-3 Solvay propoxylate/ethoxylate Tween ® 80 Sorbitan monooleate, 9005-65-6 Croda ethoxylated (20EO) Tween ® 85 Sorbitan trioleate, 9005-70-3 Croda ethoxylated (20EO) Tween ® 20 Sorbitan monolaurate, 9005-64-5 Croda ethoxylated (20EO) Genapol C 100 Alcohols, coco, 61791-13-7 Clariant ethoxylated

TABLE MAT5 Exemplified trade names of preferred wash-off reducing materials (e) Product Chemical name Tg MFFT Supplier Atplus ® FA Aqueous styrene <30° C. Croda acrylic co-polymer emulsion dispersion Acronal ®V215 aqueous acrylate −43° C. BASF Acronal ® V115 co-polymer −58° C. Acronal ® A245 dispersion containing −45° C. Acronal ® A240 carboxylic groups. −30° C. Acronal ® A225 −45° C. Acronal ® A145 −45° C. Acronal ® 500 D aqueous acrylic co- −13º C. BASF Acronal ® S 201 polymer dispersion −25° C. Acronal ® aqueous acrylic ester −40° C. BASF DS 3618 co-polymer dispersion +12º C. Acronal ® 3612 Acronal ® V 212 −40° C. Acronal ®  +4° C. DS 3502 Acronal ® S 400  −8° C. Licomer ® aqueous acrylic ester <30° C. Michelman ADH205 co-polymer dispersion Licomer ® containing carboxylic ADH203 groups. Primal ® Aqueous acrylic DOW CM-160 copolymer Primal ® emulsion polymer CM-330 Axilat ® Aqueous acrylic −15° C. 0° C. Synthomer UltraGreen 5500 emulsion polymer Povol ® 26/88 Polyvinyl alcohol Kuraray

TABLE MAT6 Exemplified trade names and CAS-No's of preferred compounds (f) Product Chemical name Cas No. Supplier Synperonic ® block-copolymer of polyethylene 9003-11-6 Croda PE/F127 oxide and polypropylene oxide Synperonic ® block-copolymer of polyethylene 9003-11-6 Croda PE/L62 oxide and polypropylene oxide Xanthan Polysaccharide 11138-66-2 Proxel ® GXL 1.2-benzisothiazol-3(2H)-one 2634-33-5 Arch Chemicals Kathon ® CG/ICP 5-chloro-2-methyl-4-isothiazolin- 26172-55-4 plus Dow 3-one plus 2-methyl-4- 2682-20-4 isothiazolin-3-one Propylene glycol 1,2-Propylene glycol 57-55-6 Glycerol Propane-1,2,3-triol 56-81-5 SAG ® 1572 Dimethyl siloxanes and silicones 63148-62-9 Momentive Atlox ® 4913 methyl methacrylate graft 119724-54-8 Croda copolymer with polyethylene glycol Atlox ® 4894 Fatty Alcohol Ethoxylate 68131-39-5 Croda Atlas ® G 5000 Oxirane, methyl-, polymer with 9038-95-3 Croda oxirane, monobutyl ether Geropon ® T36 Sodium polycarboxylate 37199-81-8 Solvay Lucramul ® PS 29 Poly(oxy-1,2-ethanediyl),. alpha.- 104376-75-2 Levaco phenyl-.omega.-hydroxy-, styrenated Soprophor ® TS/29 Poly(oxy-1,2-ethanediyl),. alpha.- 104376-75-2 Solvay phenyl-.omega.- hydroxy-, styrenated Soprophor ® TS/54 Poly(oxy-1,2-ethanediyl),. alpha.- 104376-75-2 Solvay phenyl-.omega.-hydroxy-, styrenated Morwet ® IP Naphthalenesulfonic acid, bis 68909-82-0 Akzo Nobel (1-methylethyl)-, Me derivs., sodium salts Van Gel ® B Smectite-group minerals 12199-37-0 Vanderbilt Veegum ® R Aerosil R972 Silane, dichlorodimethyl-, 68611-44-9 Evonik reaction products with silica Silcolapse ® 454 Polydimethylsiloxanes and silica 9016-00-6 Bluestar Silicones Silcolapse ® 426R Polydimethylsiloxanes and silica 9016-00-6 Bluestar Silicones Rhodopol ® 23 Polysaccharide 11138-66-2 Solvay Acticide ® MBS Mixture of 2-methyl-4- 2682-20-4 Thor GmbH isothiazolin-3-one (MIT) 2634-33-5 and 1,2-benzisothiazolin- 3-one (BIT) in water Sokalan ® K 30 Polyvinylpyrrolidone 9003-39-8 BASF Supragil ® WP Sodium diisopropyl 1322-93-6 Solvay naphthalene sulfonate Morwet ® D-425 Sodium naphthalene 577773-56-9 Akzo Nobel, sulphonate formaldehyde 68425-94-5 Nouryon condensate 9008-63-3 Soprophor ® 4 D 384 Tristyrylphenol ethoxylate 119432-41-6 Solvay sulfate (16 EO) ammonium salt Soprophor ® FLK Poly(oxy-1,2-ethanediyl), 163436-84-8 Solvay alpha.-2,4,6-tris(1- phenylethyl)phenyl-.omega.- hydroxy-, phosphate, potassium salt Rhodorsil ® Antim absorbed poly unknown Solvay EP 6703 (dimethylsiloxane) antifoam Kaolin Tec 1 Aluminium hydrosilicate 1318-74-7 Ziegler & Co. 1332-58-7 GmbH Sipernat ® 22 S synthetic amorphous silica 112926-00-8 Evonik (silicon dioxide) 7631-86-9 Rhodacal ® 60 BE Calcium- 26264-06-2 Solvay dodecylbenzenesulphonate 104-76-7 in 2-Ethylhexanol Sodium hydrogen Na2HPO4 7558-79-4 phosphate Sodium dihydrogen NaH2PO4 7558-80-7 phosphate Citric Acid C6H8O7 77-92-9 Glycerine C3H8O3 56-81-5 Urea CH4N2O 57-13-6 Supragil WP Sodium diisopropyl 1322-93-6 Solvay naphthalene sulfonate Morwet D-425 Naphthalene sulphonate 9008-63-3 Nouryon formaldehyde condensate Na salt Sokalan K 30 Polyvinylpyrrolidone 9003-39-8 BASF Silcolapse 454 Polydimethylsiloxane 7631-86-9 Solvay 9016-00-6 Sipernat 50 S synthetic amorphous silica 112926-00-8 Evonik (silicon dioxide) 7631-86-9 Kaolin Tec 1 Aluminiumhydrosilicate 1318-74-7 Ziegler & Co. 1332-58-7 GmbH

Fungicide Examples

Example FN1: Trifloxystrobin 20 SC

TABLE FN1.1 Recipes FN1.1, FN1.2 and FN1.3. Recipe Recipe FN1.2 Recipe FN1.1 according to FN1.3 Component (g/l) reference the invention reference Trifloxystrobin 20.0 20.0 20.0 Morwet ® D425 5.0 5.0 5.0 Atlox ® 4913 10.0 10.0 10.0 Synperonic ® PE/F127 5.0 5.0 5.0 Corn oil 0.0 6.0 6.0 Alkamuls ® A 0.0 50.0 50.0 Atplus ® FA 0.0 40.0 0.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 Propylene glycol 60.0 60.0 60.0 SAG ® 1572 6.0 6.0 6.0 Na2HPO4 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume (~891) (~795) (~835)

The method of preparation used was according to Method 1.

Greenhouse

TABLE FN1.2 Biological efficacy on PHAKPA/soybean. Recipe FN1.2 Recipe FN1.1 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 0.5 10 41 60 200 0.25 5 29 35 200 0.05 1 11 6  10 0.5 10 41 56  10 0.25 5 33 43  10 0.05 1 1 8

Method 12: Soybean, 1 Day Protective, Evaluation 7 Dat

The results show that recipe FN1.2 illustrative of the invention shows higher efficacy at both 10 and 200 l/ha spray volume than the reference recipe FN1.1.

Leaf Wash-Off

The wash-off was determined according to method 15.

TABLE FN1.3 Leaf wash-off data. Amount of deposit remaining after Recipe 1h on corn leaves Recipe FN1.1 not according to the invention −10 l/ha ++ Recipe FN1.1 not according to the invention −200 l/ha +++++ Recipe FN1.2 according to the invention −10 l/ha +++ Recipe FN1.2 according to the invention −200 l/ha +++++ Recipe FN1.3 not according to the invention −10 l/ha + Recipe FN1.3 not according to the invention −200 l/ha +++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN1.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipes FN1.1 and FN1.3 containing uptake enhancing additive (d) but without rainfast additive (e).

Example FN2: Inpyrfuxam SC

TABLE FN2.1 Recipes FN2.1, FN2.2, FN2.3, FN2.4 and FN2.5. Recipe Recipe Recipe FN2.2 Recipe Recipe FN2.5 FN2.1 according FN2.3 FN2.4 according refer- to the refer- refer- to the Component (g/l) ence invention ence ence invention Inpyrfluxam 80.0 80.0 80.0 10.0 10.0 Morwet ® D425 5.0 5.0 5.0 5.0 5.0 Synperonic ® 10.0 10.0 10.0 5.0 5.0 PE/F127 Atlox ® 4913 10.0 10.0 10.0 5.0 5.0 Soybean oil 0.0 10.0 10.0 0.0 10.0 Silwet ® 408 0.0 40.0 40.0 0.0 0.0 Silwet ® 806 0.0 0.0 0.0 0.0 30.0 Alkamuls ® A 0.0 60.0 60.0 0.0 40.0 Licomer ® 0.0 0.0 0.0 0.0 25.0 ADH 205 Atplus ® FA 0.0 50.0 0.0 0.0 0.0 Xanthan 3.0 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 1.8 Kathon ® 0.8 0.8 0.8 0.8 0.8 CG/ICP Propylene glycol 60.0 60.0 60.0 80.0 80.0 SAG ® 1572 6.0 6.0 6.0 6.0 6.0 Na2HPO4 (Buffer 1.5 1.5 1.5 1.5 1.5 solution pH = 7) NaH2PO4 (Buffer 0.8 0.8 0.8 0.8 0.8 solution pH = 7) Water To To To To To (add to 1 litre) volume volume volume volume volume (~866) (~746) (~796) (~886) (~811)

The method of preparation used was according to Method 1.

Greenhouse

TABLE FN2.2 Biological efficacy on PHAKPA/soybean. Recipe FN2.5 Recipe FN2.4 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 0.2 2 69 65 200 0.1 1 38 39 200 0.05 0.5 31 28  10 0.2 2 76 85  10 0.1 1 57 60  10 0.05 0.5 42 42

Method 12: Soybean, 1 Day Protective, Evaluation 7 Dat

The results show that recipe FN2.5 illustrative of the invention shows comparable or higher efficacy at both 10 and 200 l/ha spray volume compared to the reference recipe FN2.4. Furthermore, recipe FN2.5 shows higher efficacy at 10 l/ha compared to 200 l/ha.

Cuticle Penetration

The penetration through apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE FN2.3 Cuticle penetration for inpyrfluxam SC formulations. Uptake Uptake enhancing enhancing agent dose agent in spray Penetration Penetration dose liquid Recipe % 17h % 45h g/ha % w/v Recipe FN2.1 not 10.4 29.9 0 0 according to the invention - 10 l/ha Recipe FN2.1 not 12.6 24.8 0 0 according to the invention - 200 l/ha Recipe FN2.2 29.7 57.1 30 0.3 according to the invention - 10 l/ha Recipe FN2.2 21.9 37.9 30 0.015 according to the invention - 200 l/ha

Formulations tested at 0.5 l/ha.

The results show that recipe FN2.2 illustrative of the invention has a higher cuticle penetration than the reference recipe FN2.1 at both 10 l/ha and 200 l/ha. Furthermore, recipe FN2.2 has a higher penetration at 10 l/ha compared to 200 l/ha.

Leaf Wash-Off

The wash-off was determined according to method 15.

TABLE FN2.4 Leaf wash-off data. Amount of deposit remaining after Recipe 1h on corn leaves Recipe FN2.1 not according to the invention - 10 l/ha +++ Recipe FN2.1 not according to the invention - 200 l/ha +++++ Recipe FN2.2 according to the invention - 10 l/ha ++++ Recipe FN2.2 according to the invention - 200 l/ha +++++ Recipe FN2.3not according to the invention - 10 1/ha ++ Recipe FN2.3 not according to the invention - 200 l/ha +++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN2.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipe FN2.1 and a higher amount of applied formulation remaining at 10 and 200 l/ha compared to recipe FN2.2 containing drift reducing additive (b) and uptake enhancing additive (d) but without rainfast additive (e).

Example FN3: Fluopyram 200 SC

TABLE FN3.1 Recipes FN3.1, FN3.2, and FN3.3. Recipe FN3.2 Recipe FN3.1 according Recipe FN3.3 Component (g/l) reference to the invention reference Fluopyram 200.0 200.0 200.0 Morwet ® D425 5.0 5.0 5.0 Synperonic ® PE/F127 20.0 20.0 20.0 Geropon ® T36 5.0 5.0 5.0 Rapeseed oil methyl ester 0.0 12.0 0.0 Alkamuls ® A 0.0 70.0 70.0 Atplus ® FA 0.0 60.0 60.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Acticide ® SPX 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 SAG ® 1572 6.0 6.0 6.0 Na2HPO4 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume (~761) (~619) (~631)

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 7.

TABLE FN3.2 Drift data for fluopyram SC recipes. Relative amount Relative amount Concen- of driftable of driftable Concen- tration fraction of spray fraction of spray tration of drift Dose of droplets <100 droplets <150 of drift reducing drift microns from microns from reducing oil (b) reducing Spray recipe FN3.2 recipe FN3.2 oil (b) in spray oil (b) volume compared to compared to in recipe liquid in target l/ha recipe FN3.3% recipe FN3.3% g/l % w/v crop g/ha 20 94.0 98.3 12.0 0.003 6.0

Formulations tested at 0.5 l/ha.

The results show that recipes FN3.2 illustrative of the invention shows a lower amount of driftable fraction of spray droplets less than 100 microns at 20 l/ha spray volume compared to the reference recipe FN3.3 without drift reducing oil (b).

Leaf Wash-Off

The wash-off was determined according to method 13.

TABLE FN3.3 Leaf wash-off data. Amount of deposit remaining Recipe after 1h on corn leaves Recipe FN3.2 according to the invention −20 l/ha Recipe FN3.3 not according to the invention −20 l/ha Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN3.2 illustrative of the invention shows a higher amount of applied formulation remaining at 20 L/ha spray volume compared to the reference recipe FN3.3 without rainfast agent (e).

Example FN4: Prothioconazole 20 SC

TABLE FN4.1 Recipes FN4.1 and FN4.2. Recipe FN4.1 Recipe FN4.2 according Component (g/l) reference to the invention Prothioconazole 20.0 20.0 Morwet ® D425 5.0 5.0 Atlox ® 4913 12.0 12.0 Synperonic ® PE/F127 5.0 5.0 Rapeseed oil 0.0 10.0 Synperonic ® A7 0.0 60.0 Atplus ® FA 0.0 40.0 Xanthan 3.0 3.0 Van Gel ® B 5.0 5.0 Proxel ® GXL 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 Propylene glycol 60.0 60.0 SAG ® 1572 6.0 6.0 Na2HPO4 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume (~889) (~779)

The method of preparation used was according to Method 1.

Greenhouse

TABLE FN4.3 Biological efficacy on PHAKPA/soybean. Recipe FN4.2 Recipe FN4.1 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 0.05 1 96 99 200 0.025 0.5 25 50 200 0.0125 0.25 1 1  10 0.05 1 98 93  10 0.025 0.5 55 54  10 0.0125 0.25 9 13

Method 12: Soybean, 1 Day Protective, Evaluation 7 Dat

The results show that recipe FN4.2 illustrative of the invention shows higher efficacy at 200 l/ha spray volume and comparably efficacy at 10 l/ha than the reference recipe FN4.1.

Example FN5: Fluoxapiprolin 40 SC

TABLE FN5.1 Recipes FN5.1, FN5.2, FN5.3, FN5.4, FN5.5, FN5.6 and FN5.7. Recipe Recipe Recipe Recipe Recipe Recipe FN5.5 FN5.6 FN5.7 FN5.2 FN5.3 FN5.4 containing containing containing containing containing containing drift drift drift Recipe drift drift drift reducing reducing reducing Component FN5.1 reducing reducing reducing oil oil oil (g/l) reference oil (b) oil (b) oil (b) (b) (b) (b) Fluoxapiprolin 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Morwet ® 5.0 5.0 5.0 5.0 5.0 5.0 5.0 D425 Synperonic ® 20.0 20.0 20.0 20.0 20.0 20.0 20.0 PE/F127 Rapeseed oil 0.0 0.1 1.0 10.0 20.0 50.0 100.0 methyl ester Xanthan 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Kathon ® 0.8 0.8 0.8 0.8 0.8 0.8 0.8 CG/ICP Propylene 80.0 80.0 80.0 80.0 80.0 80.0 80.0 glycol SAG ® 1572 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Na2HPO4 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to To To To To To To To 1 litre) volume volume volume volume volume volume volume (~861) (~861) (~860) (~851) (~841) (~801) (~751)

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 7.

TABLE FN5.2 Drift data for fluoxapiprolin SC recipes. Relative amount Relative amount of driftable of driftable fraction of spray fraction of spray Concentration droplets <100 droplets <150 Concentration of drift microns from microns from of drift reducing oil Dose of drift recipe compared recipe compared reducing oil (b) in spray reducing oil to recipe FN5.1 to recipe FN5.1 (b) in recipe liquid (b) in target Recipe % % g/l % w/v crop g/ha FN5.1 100.0 100.0 0.0 0.0 0.0 FN5.2 103.3 100.0 0.1 0.00025 0.05 FN5.3 80.0 87.7 1.0 0.0025 0.5 FN5.4 50.0 64.9 10.0 0.025 5.0 FN5.5 53.3 66.7 20.0 0.05 10.0 FN5.6 60.0 77.2 50.0 0.125 25.0 FN5.7 46.7 66.7 100.0 0.25 50.0

Formulations tested at 0.5 l/ha.

The results show that recipes FN5.3, FN5.4 and FN5.5 illustrative of the inventive dose of drift reducing oil (b) show a lower amount of driftable fraction of spray droplets less than 100 microns and less than 150 microns at 20 l/ha spray volume compared to the reference recipe FN5.1 without drift reducing oil (b). Furthermore, the low amount of drift reducing oil in recipes FN5.4 and FN5.5 achieves the same level of reduction in the amount of the driftable fraction of spray droplets less than 100 microns and less than 150 microns compared to recipes FN5.6 and FN5.7 which contain significantly higher amounts of drift reducing oil (b).

Example FN6: Bixafen 50 SC

TABLE FN6.1 Recipes FN6.1, FN6.2 and FN6.3. Recipe Recipe FN6.2 FN6.1 according to Recipe FN6.3 Component (g/l) reference the invention reference Bixafen 50.0 50.0 50.0 Morwet ® D425 5.0 5.0 5.0 Atlox ® 4913 10.0 10.0 10.0 Synperonic ® PE/F127 10.0 10.0 10.0 Crodamol ® OP 0.0 12.0 0.0 Lucramol ® HOT 5902 0.0 60.0 60.0 Licomer ® ADH205 0.0 50.0 50.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 Propylene glycol 60.0 60.0 60.0 SAG ® 1572 6.0 6.0 6.0 Na2HPO4 (Buffer solution 1.5 1.5 1.5 pH = 7) NaH2PO4 (Buffer solution 0.8 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume To volume (~886) (~764) (~776)

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 7.

TABLE FN8.2 Drift data. Relative amount Relative amount of driftable of driftable fraction of fraction of spray spray droplets droplets <100 <150 microns microns from from recipe Concentration Concentration recipe FN8..2 FN8.2 of drift of drift reducing Dose of drift Spray compared to compared to reducing oil oil (b) in spray reducing oil volume recipe FN8.3 recipe FN8.3 (b) in recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 20 68.3 82.2 12 0.003 6

Formulations tested at 0.5 l/ha.

The results show that recipe FN8.2 illustrative of the invention show a lower driftable droplet fraction at 20 l/ha spray volume compared to the reference recipe FN8.3 without drift reducing oil (b).

Greenhouse

TABLE FN6.3 Biological efficacy on PHAKPA/soybean. Recipe FN6.2 Recipe FN6.1 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 0.5 25 15 66 200 0.25 12.5 3 15 200 0.125 6.25 3 2 10 0.5 25 23 28 10 0.25 12.5 8 25 10 0.125 6.25 12 2

Method 12: Soybean, 1 Day Protective, Evaluation 7 Dat

The results show that recipe FN6.2 illustrative of the invention shows higher efficacy at both 10 and 200 l/ha spray volume compared to the reference recipe FN6.1.

Leaf Wash-Off

The wash-off was determined according to method 15.

TABLE FN6.4 Leaf wash-off data. Amount of deposit remaining after 1 h on Recipe corn leaves Recipe FN6.1 not according to the invention - 10 l/ha ++ Recipe FN6.1 not according to the invention - 200 l/ha +++++ Recipe FN6.2 according to the invention - 10 l/ha ++++ Recipe FN6.2 according to the invention - 200 l/ha +++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN6.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipe FN6.1.

Example FN7: Fluopicolide 150 SC

TABLE FN7.1 Recipes FN7.1, FN7.2, FN7.3 and FN7.4. Recipe FN7.2 Recipe according Recipe Recipe FN7.1 to the FN7.3 FN7.4 Component (g/l) reference invention reference reference Fluopicolide 150.0 150.0 150.0 150.0 Morwet ® D425 5.0 5.0 5.0 5.0 Synperonic ® 15.0 15.0 15.0 15.0 PE/F127 Soprophor ® FLK 10.0 10.0 10.0 10.0 Crodamol ® OP 0.0 20.0 20.0 20.0 Crovol ® CR70G 0.0 130.0 0.0 130.0 Atplus ® FA 0.0 65.0 0.0 0.0 Xanthan 4.0 4.0 4.5 4.0 Proxel ® GXL 1.5 1.5 1.5 1.5 Acticide ® SPX 0.8 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 80.0 SAG ® 1572 4.0 4.0 4.0 4.0 Na2HPO4 (Buffer 0.0 1.5 0.0 1.5 solution pH = 7) NaH2PO4 (Buffer 0.0 0.8 0.0 0.8 solution pH = 7) Water (add to 1 To To To To litre) volume volume volume volume (~820) (~605) (~799) (~670)

The method of preparation used was according to Method 1.

Cuticle Penetration

The penetration through apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE FN7 Cuticle penetration for fluopicolide SC formulations. Uptake Uptake enhancing agent enhancing agent dose in spray Penetration % Penetration % dose liquid Recipe 26 h 47 h g/ha % w/v Recipe FN7.1 not according 5.8 7.5 0 0 to the invention - 10 l/ha Recipe FN7.1 not according 4.5 9.0 0 0 to the invention - 200 l/ha Recipe FN7.2 according to 17.8 26.8 65 0.65 the invention - 10 l/ha Recipe FN7.2 according to 10.6 17.0 65 0.0325 the invention - 200 l/ha Recipe FN7.3 not according 5.0 7.8 0 0 to the invention - 10 l/ha Recipe FN7.3 not according 5.0 7.5 0 0 to the invention - 200 l/ha

Formulations tested at 0.5 l/ha.

The results show that recipe FN7.2 illustrative of the invention has a higher cuticle penetration than the reference recipe FN7.1 at both 10l/ha and 200 l/ha. Furthermore, recipe FN7.2 has a higher penetration at 10 l/ha compared to 200 l/ha. In addition, recipe FN7.3 which contains a low amount of oil based drift reducing agent (Crodamol® OP) has comparable cuticle penetration to the reference recipe FN7.1 without any oil based drift reducing agent, demonstrating that the small amount of oil does not enhance the cuticle penetration and is not present at a level that affects the biodelivery of the active ingredient.

Leaf Wash-Off

The wash-off was determined according to method 15.

TABLE FN7.4 Leaf wash-off data. Amount of deposit remaining after 1 h on Recipe corn leaves Recipe FN7.1 not according to the invention - 10 l/ha +++ Recipe FN7.1 not according to the invention - 200 l/ha ++++ Recipe FN7.2 according to the invention - 10 l/ha ++ Recipe FN7.2 according to the invention - 200 l/ha ++++ Recipe FN7.4 not according to the invention - 10 l/ha + Recipe FN7.4 not according to the invention - 200 l/ha ++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN7.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipe FN7.4 with the uptake enhancing agent (d) and without the rainfast agent (e).

Example FN8: Isoflucypram 10 SC

TABLE FN8.1 Recipes FN8.1 and FN8.2. Recipe Recipe FN8.2 FN8.1 according to Component (g/l) reference the invention Isoflucypram 20.0 20.0 Morwet ® D425 5.0 5.0 Atlox ® 4913 10.0 10.0 Synperonic® PE/F127 5.0 5.0 Corn oil 0.0 15.0 Alkamuls ® A 0.0 50.0 Atplus ® FA 0.0 50.0 Xanthan 3.0 3.0 Van Gel ® B 5.0 5.0 Proxel ® GXL 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 Glycerine 60.0 60.0 SAG ® 1572 6.0 6.0 Na2HPO4 (Buffer solution pH = 7) 1.5 1.5 NaH2PO4 (Buffer solution pH = 7) 0.8 0.8 Water (add to 1 litre) To volume To volume (~891) (~776)

The method of preparation used was according to Method 1.

Greenhouse

TABLE FN8.3 Biological efficacy on PUCCRT/wheat. Recipe FN8.2 Recipe FN8.1 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 1.0 20 13 38 200 0.5 10 8 17 200 0.25 5 0 42 10 1.0 20 8 54 10 0.5 10 0 38 10 0.25 5 0 13

Method 12: Wheat, 2 Day Curative, Evaluation 7 Dat.

The results show that recipe FN8.2 illustrative of the invention shows higher efficacy at both 10 and 200 l/ha spray volume than the reference recipe FN8.1. Furthermore, recipe FN8.2 shows higher efficacy at 10 l/ha compared to 200 l/ha.

Images of the leaf deposits on sprayed wheat plants are shown in FIG. 1 and show that both recipe FN8.2 illustrative of the invention and the reference recipe FN8.1 show poor coverage at 10 l/ha as expected for a spray applied at a low spray volume. It is surprising how recipe FN8.2 illustrative of the invention shows significantly higher efficacy here illustrating that the uptake of the active ingredient by the uptake enhancing agent at low spray volumes has a surprisingly good biological effect.

Leaf Wash-Off

The wash-off was determined according to method 13.

TABLE FN8.4 Leaf wash-off data. Amount of deposit remaining after 1h on Recipe corn leaves Recipe FN8.1 not according to the invention - 10 l/ha +++ Recipe FN8.1 not according to the invention - 200 l/ha ++++ Recipe FN8.2 according to the invention - 10 l/ha ++++ Recipe FN8.2 according to the invention - 200 l/ha +++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe FN8.2 illustrative of the invention shows a higher amount of applied formulation remaining at both 10 and 200 L/ha spray volume compared to the reference recipe FN8.1.

Example FN9: Fluoxapiprolin 10 SC

TABLE FN9.1 Recipes FN9.1 and FN9.2. Recipe Recipe FN9.2 FN9.1 according to Recipe FN9.3 Component (g/l) reference the invention reference Fluoxapiprolin 10.0 10.0 10.0 Morwet ® D425 5.0 5.0 5.0 Atlox® 4913 5.0 5.0 5.0 Synperonic ® PE/F127 5.0 5.0 5.0 Rapeseed oil methyl ester 0.0 12.0 0.0 Alkamuls ® A 0.0 60.0 60.0 Licomer ® ADH205 0.0 40.0 40.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 Propylene glycol 80.0 80.0 60.0 SAG ® 1572 6.0 6.0 6.0 Na2HPO4 (Buffer solution 1.5 1.5 1.5 pH = 7) NaH2PO4 (Buffer solution 0.8 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume To volume (~886) (~774) (~786)

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 9.

TABLE FN9.2 Drift data for fluoxapiprolin SC recipes. Amount of driftable Amount of driftable fraction (at % vol fraction (at % vol <100 microns) from <100 microns) from recipe FN9.2 recipe FN9.2 according to the according to thei invention compared nvention compared to to recipe FN9.1 not recipe FN9.3 not according to the according to the Spray volume invention % invention % 10 1/ha 64 78

Formulations tested at 0.35 l/ha.

The results show that recipe FN9.2 illustrative of the invention shows a lower driftable fraction of spray droplets at 10 L/ha spray volume compared to the reference recipe FN9.1 and reference recipe FN9.3 without drift reducing oil (b).

Greenhouse

TABLE FN9.3 Biological efficacy on PHYTIN / tomato. Recipe FN9.2 Recipe FN9.1 according to the Spray volume Rate of SC Rate of a.i. reference invention l/ha applied l/ha g/ha Efficacy [%] Efficacy [%] 200 1 10 69 79 200 0.5 5 56 67 200 0.25 2.5 15 70 15 1 10 24 47 15 0.5 5 24 36 15 0.25 2.5 12 27

Method 12: Tomato, 1 Day Curative, Evaluation 4 Dat

The results show that the reference recipe FN9.1 shows a large decrease in efficacy on reducing the spray volume from 200 l/ha to 15 l/ha. The recipe FN9.2 illustrative of the invention maintains a markedly better efficacy as the spray volume is decreased from 200 l/ha to 15 l/ha. Furthermore, recipe FN9.2 shows higher efficacy at both 15 l/ha spray volume compared to the reference recipe FN9.1.

Images of the leaf deposits on sprayed tomato plants are shown in FIG. 2 and show that both recipe FN9.2 illustrative of the invention and the reference recipe FN9.1 show poor coverage at 15 l/ha as expected for a spray applied at a low spray volume. It is surprising how recipe FN9.2 illustrative of the invention shows significantly higher efficacy here illustrating that the uptake of the active ingredient by the uptake enhancing agent at low spray volumes has a surprisingly good biological effect.

Example FN10: Fluopicolide SC

TABLE FN10.1 Recipes FN10.1, FN10.2, FN10.3 and FN10.4. Recipe FN10.2 Recipe according Recipe Recipe FN10.1 to the FN10.3 FN10.4 Component (g/l) reference invention reference reference Fluopicolide 20.0 20.0 20.0 20.0 Morwet ® D425 5.0 5.0 5.0 5.0 Synperonic ® PE/ 8.0 8.0 8.0 8.0 F127 AgRho ® DR2000 0.0 6.0 0.0 12.0 Alkamuls ® A 0.0 50.0 50.0 0.0 Licomer ® ADH205 0.0 20.0 20.0 0.0 Xanthan 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 80.0 SAG ® 1572 8.0 8.0 8.0 8.0 Na2HPO4 1.5 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To To volume To volume To volume volume (~800) (~806) (~864) (~876)

The method of preparation used was according to Method 2.

Spreading on Tomato Plants

Tomato plants at the 4 leaf growth stage (BBCH 14) were sprayed with a TeeJet® TP8002E nozzle at a pressure of 2 bar. A PWM device was used to achieve the spray volume of 15 l/ha. A small amount of a fluorescent marker was added to the spray liquid and the % coverage was determined under UV illumination (365 nm) visually.

TABLE FN10.2 Spray % coverage on tomato plants. Spreading agent dose Spreading in spray Deposit area agent dose liquid Recipe coverage % g/ha % w/v Recipe FN10.1 not according 10 0 0 to the invention-15 l/ha Recipe FN10.1 not according 50 0 0 to the invention-200 l/ha Recipe FN10.2 according 10 50 0.333 to the invention-15 l/ha Recipe FN10.2 according 50 50 0.025 to the invention-200 l/ha

Formulations applied at 1.0 l/ha.

The results show that recipe FN10.2 illustrative of the invention shows comparable leaf coverage compared to the reference recipe FN10.1 at both 15 l/ha and 200 l/ha spray volumes.

Greenhouse

TABLE FN10.3 Biological efficacy on PHYTIN/tomato. Recipe FN10.2 Recipe according Rate FN10.1 to the Spray of SC Rate reference invention volume applied of a.i. Efficacy Efficacy l/ha l/ha g/ha [%] [%] 200 1 20 81 96 200 0.5 10 25 60 200 0.25 5 11 33  15 1 20 15 71  15 0.5 10 34 52  15 0.25 5 12 14

Method 12: Tomato, 1 Day Curative, Evaluation 4 Dat

The results show that the recipe FN10.2 illustrative of the invention demonstrates a better efficacy compared to the reference recipe FN10.1 at both 200 l/ha and 15 l/ha. Furthermore, the efficacy of recipe FN10.2 is surprisingly high at 15 l/ha for the lower coverage observed (Table FN10.3) compared to 200 l/ha, demonstrating the benefit of the uptake enhancing agent (d) at 15 l/ha spray volume.

Physical Aspect

The physical aspect with regard to viscosity was assessed visually.

TABLE FN10.4 Physical aspect of recipes. Drift reducing polymer (b) concentration in recipe Recipe g/l Physical aspect Recipe FN10.1 0.0 Fluid pourable not according suspension. to the invention Recipe FN10.2 6.0 Fluid pourable according suspension. to the invention Recipe FN10.3 0.0 Fluid pourable not according suspension. to the invention Recipe FN10.4 12.0 Highly viscous not according suspension, to the invention difficult to pour.

The results show that recipe FN10.4 is too viscous for use by customers and illustrates that there is an upper concentration limit for how much polymer can be incorporated in an SC recipe. For the drift reducing polymer AgRho DR2000 this is approximately 10 g/l.

Example FN11: Inpyrfluxam SC

TABLE FN11.1 Recipes FN11.1, FN11.2 and FN11.3 Recipe FN11.2 Recipe according Recipe FN11.1 to the FN11.3 Component (g/l) reference invention reference Inpyrfluxam 100.0 100.0 100.0 Morwet ® D425 5.0 5.0 5.0 Atlox ® 4913 10.0 10.0 10.0 Synperonic ® PE/F127 10.0 10.0 10.0 Sunflower oil 0.0 16.0 0.0 Crovol ® CR70G 0.0 50.0 50.0 Licomer ® ADH 205 0.0 30.0 30.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Acticide ® SPX 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 SAG ® 1572 6.0 6.0 6.0 Na2HPO4 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume (~836) (~740) (~756)

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 7.

TABLE FN11.2 Drift data. Relative amount Relative amount of driftable of driftable fraction of fraction of spray droplets spray droplets Concentration <100 microns <150 microns Concentration of drift from recipe from recipe of drift reducing FN11.2 FN11.2 reducing oil (b) Dose of drift Spray compared to compared to oil (b) in in spray reducing oil volume recipe FN11.3 recipe FN11.3 recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 20 46.2 64.3 16.0 0.04 8.0

Formulations tested at 0.5 l/ha.

The results show that recipe FN11.2 illustrative of the invention show a lower driftable droplet fraction at 20 l/ha spray volume compared to the reference recipe FN11.3 without drift reducing oil (b).

Example FN12: Fluoxapiprolin SC

TABLE FN12.1 Recipes FN12.1, FN12.2 and FN12.3 Recipe FN12.2 Recipe according Recipe FN12.1 to the FN12.3 Component (g/l) reference invention reference Fluoxapiprolin 50.0 50.0 50.0 Morwet ® D425 5.0 5.0 5.0 Soprophor ® FLK 8.0 8.0 8.0 Synperonic ® PE/F127 10.0 10.0 10.0 Polyox ® WSR N60K 0.0 2.2 0.0 Crovol ® CR70G 0.0 50.0 50.0 Licomer ® ADH 205 0.0 20.0 20.0 Xanthan 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 Acticide ® SPX 0.8 0.8 0.8 Glycerine 70.0 70.0 70.0 SAG ® 1572 8.0 8.0 8.0 Na2HPO4 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume (~866) (~794) (~796)

The method of preparation used was according to Method 2.

Drift

The drift was determined according to method 7.

TABLE FN12.2 Drift data. Relative amount Relative amount of driftable of driftable fraction of fraction of spray droplets spray droplets Concentration <100 microns <150 microns Concentration of drift from recipe from recipe of drift reducing FN12.2 FN12.2 reducing oil (b) Dose of drift Spray compared to compared to polymer in spray reducing oil volume recipe FN12.3 recipe FN12.3 (b) in recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 20 65.9 78.9 2.2 0.0055 1.1

Formulations tested at 0.5 l/ha.

The results show that recipe FN12.2 illustrative of the invention show a lower driftable droplet fraction at 20 l/ha spray volume compared to the reference recipe FN12.3 without drift reducing polymer (b).

Example FN16: Bixafen SC

TABLE FN16.1 Recipes FN16.1, FN16.2, FN16.3, FN16.4 and FN16.5. Recipe Recipe Recipe Recipe FN16.2 FN16.3 FN16.4 FN16.5 containing containing containing containing drift drift drift drift Recipe reducing reducing reducing reducing FN16.1 polymer polymer polymer polymer Component (g/l) reference (b) (b) (b) (b) Bixafen 100.0 100.0 100.0 100.0 100.0 Morwet ® D425 5.0 5.0 5.0 5.0 5.0 Atlox ® 4913 20.0 20.0 20.0 20.0 20.0 Synperonic ® PE/F127 5.0 5.0 5.0 5.0 5.0 Polyox ® WSR 301 0.0 0.3 0.6 0.9 1.2 Silwet ® L77 0.0 0.0 0.0 0.0 0.0 Crovol ® CR70G 0.0 0.0 0.0 0.0 0.0 Xanthan 3.0 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 80.0 80.0 SAG ® 1572 8.0 8.0 8.0 8.0 8.0 Na2HPO4 1.5 1.5 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume To volume To volume (~831) (~831) (~830) (~830) (~830)

The method of preparation used was according to Method 2.

Physical Aspect

The physical aspect with regard to viscosity was assessed visually.

TABLE FN16.4 Physical aspect of recipes. Drift reducing polymer (b) concentration in recipe Recipe g/l Physical aspect FN16.1 0.0 Fluid pourable suspension. FN16.2 0.3 Fluid pourable suspension. FN16.3 0.6 Fluid pourable suspension. FN16.4 0.9 Fluid pourable suspension. FN16.5 1.2 Fluid pourable suspension.

The results show that the polymer Polyox® WSR301 can be incorporated into SC recipes over the concentration range of 0.3 to 1.2 g/L.

Spray Droplet Size

The spray droplet size was determined according to method 9.

TABLE FN16.4 Driftable fraction of spray droplets. Amount of Amount of driftable driftable droplet droplet fraction fraction (at % vol (at % vol Drift reducing <100 microns) <150 microns) polymer (b) from recipe from recipe concentration compared compared in recipe to recipe to recipe Recipe g/l FN16.1 % FN16.1 % FN16.1 0.0 100 100 FN16.2 0.3 99 97 FN16.3 0.6 95 93 FN16.4 0.9 80 82 FN16.5 1.2 72 77

Formulations applied at 0.5 l/ha in a spray volume of 15 l/ha.

The results show that the polymer Polyox® WSR301 can reduce the driftable fraction of spray droplets <100 microns and <150 microns over the concentration range of 0.6 to 1.2 g/L (for a recipe used at 0.5 l/ha in a spray volume of 15 l/ha).

Example FN17: Tebuconazole SC

TABLE FN17.1 Recipes FN17.1, FN17.2, FN17.3, FN17.4 and FN17.5. Recipe Recipe Recipe Recipe FN17.2 FN17.3 FN17.4 FN17.5 containing containing containing containing drift drift drift drift Recipe reducing reducing reducing reducing FN17.1 polymer polymer polymer polymer Component (g/l) reference (b) (b) (b) (b) Tebuconazole 200.0 200.0 200.0 200.0 200.0 Morwet ® D425 5.0 5.0 5.0 5.0 5.0 Atlox ® 4913 20.0 20.0 20.0 20.0 20.0 Synperonic ® PE/F127 10.0 10.0 10.0 10.0 10.0 Polyox ® WSR N12K 0.0 0.8 1.6 2.4 3.2 Crovol ® CR70G 0.0 0.0 0.0 0.0 0.0 Xanthan 3.0 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 80.0 80.0 SAG ® 1572 8.0 8.0 8.0 8.0 8.0 Na2HPO4 1.5 1.5 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume To volume To volume (~736) (~735) (~734) (~734) (~733)

The method of preparation used was according to Method 2.

TABLE FN17.2 Recipes FN17.6, FN17.7, FN17.8 and FN17.9. Recipe Recipe Recipe Recipe FN17.6 FN17.7 FN17.8 FN17.9 containing containing containing containing drift drift drift drift reducing reducing reducing reducing polymer polymer polymer polymer Component (g/l) (b) (b) (b) (b) Tebuconazole 200.0 200.0 200.0 200.0 Morwet ® D425 5.0 5.0 5.0 5.0 Atlox ® 4913 20.0 20.0 20.0 20.0 Synperonic ® PE/F127 10.0 10.0 10.0 10.0 Polyox ® WSR N12K 0.8 1.6 2.4 3.2 Crovol ® CR70G 100.0 100.0 100.0 100.0 Xanthan 3.0 3.0 3.0 3.0 Van Gel ® B 5.0 5.0 5.0 5.0 Proxel ® GXL 1.8 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 0.8 Propylene glycol 80.0 80.0 80.0 80.0 SAG ® 1572 8.0 8.0 8.0 8.0 Na2HPO4 1.5 1.5 1.5 1.5 (Buffer solution pH = 7) NaH2PO4 0.8 0.8 0.8 0.8 (Buffer solution pH = 7) Water (add to 1 litre) To volume To volume To volume To volume (~635) (~634) (~634) (~633)

The method of preparation used was according to Method 2.

Physical Aspect

The physical aspect with regard to viscosity was assessed visually.

TABLE FN17.3 Physical aspect of recipes. Drift reducing polymer (b) concentration in recipe Recipe g/l Physical aspect FN17.1 0.0 Fluid pourable suspension. FN17.2 0.6 Fluid pourable suspension. FN17.3 1.2 Fluid pourable suspension. FN17.4 1.8 Fluid pourable suspension. FN17.5 2.4 Fluid pourable suspension. FN17.6 0.6 Fluid pourable suspension. FN17.7 1.2 Fluid pourable suspension. FN17.8 1.8 Fluid pourable suspension. FN17.9 2.4 Fluid pourable suspension.

The results show that the polymer Polyox® WSR N12K can be incorporated into SC recipes over the concentration range of 0.6 to 2.4 g/L.

Spray Droplet Size

The spray droplet size was determined according to method 9.

TABLE FN17.5 Driftable fraction of spray droplets. Amount of Amount of driftable driftable droplet droplet fraction fraction (at % vol (at % vol Drift reducing <100 microns) <150 microns) polymer (b) from recipe from recipe concentration compared compared in recipe to recipe to recipe Recipe g/l FN17.1 % FN17.1 % FN17.1 0.0 100 100 FN17.2 0.6 88 94 FN17.3 1.2 75 84 FN17.4 1.8 60 67 FN17.5 2.4 55 63 FN17.6 0.6 100 100 FN17.7 1.2 91 94 FN17.8 1.8 81 92 FN17.9 2.4 88 93

Formulations applied at 0.5 l/ha in a spray volume of 15 l/ha.

The results show that the polymer Polyox® WSR N12K can reduce the driftable fraction of spray droplets <100 microns and <150 microns over the concentration range of 0.6 to 2.4 g/L (for a recipe used at 0.5 l/ha in a spray volume of 15 l/ha). Furthermore, these results demonstrate that the reduction of the driftable fraction is also observed with uptake enhancing agents (d).

Insecticide Examples

Example IN1: Spirotetramat 150 SC

TABLE IN 1.1 Recipes IN11 and IN15. Recipe Recipe IN15 IN11 according to Component (g/l) reference the invention Spirotetramat 150.0 150.0 Morwet ® D425 5.0 5.0 Soprophor TS29 30.0 30.0 Miglyol 812N 0.0 20.0 Synperonic PE/F 127 0.0 2.0 Lucramul ® Hot 5902 0.0 70.0 Licomer ® ADH205 0.0 60.0 Rhodopol 23 2.0 2.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 Glycerine 80.0 80.0 SAG ® 1572 2.0 2.0 Citric Acid 1.0 1.0 Water (add to 1 litre) To volume To volume

The method of preparation used was according to Method 1.

Pipette Spreading Tests on Leaves

The leaf deposit size was determined according to method 17.

TABLE IN1.2 Spray dilution droplet size and dose on non-textured apple leaves and textured rice leaves. Deposit Deposit Spreading Spreading area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple rice g/ha % w/v Recipe IN11 not 4.20  1.12 0 0 according to the invention—8 l/ha Recipe IN11 not 4.50  0.83 0 0 according to the invention—15 l/ha Recipe IN11 not 3.52  1.11 0 0 according to the invention—100 l/ha Recipe IN15 according to 6.14  9.88 0 0 the invention—8 l/ha Recipe IN15 according to 5.18 12.62 0 0 the invention—15 l/ha Recipe IN15 according to 6.28  8.09 0 0 the invention—100 l/ha

Formulations applied at 8/15/100l/ha.

The results show that recipe IN15 illustrative of the invention shows greater deposit sizes at 15 L/ha spray volume than at 100 L/ha and also compared to the reference recipe IN11.

Cuticle Penetration

The penetration though apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE IN1.3 Cuticle penetration for Spirotetramat SC formulations. Uptake Uptake enhancing Penetration % Penetration % enhancing agent agent dose in spray Recipe 20-25 h 45-47 h dose [g/ha] liquid [% w/v] Recipe IN11 not 2.2 6.7 0 0 according to the invention—10 l/ha Recipe IN11 not 2.6 6.1 0 0 according to the invention—200 l/ha Recipe IN15 according 12.0 33.4 35 0.35 to the invention—10 l/ha Recipe IN15 according 12.0 22.3 35 0.0175 to the invention—200 l/ha

Formulations tested at 0.5 l/ha.

The results show that recipe N15 illustrative of the invention has a higher cuticle penetration than the reference recipe IN11 at both 10 l/ha and 200 l/ha. Furthermore, recipe IN15 has a higher penetration at 10l/ha compared to 200 l/ha at 48 h.

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN1.4 Leaf wash-off data. Amount of deposit remaining after 1 h Recipe on corn leaves Recipe IN11 not according to +++ the invention—10 l/ha Recipe IN11 not according to ++++ the invention—200 l/ha Recipe IN15 according to the +++ invention—10 l/ha Recipe IN15 according to the ++++ invention—200 l/ha Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

Example IN2: Tetraniliprole 80 SC

TABLE IN 2.1 Recipes IN21, IN25 and IN85 Recipe Recipe IN25 Recipe IN85 IN21 according to according to Component (g/l) reference the invention the invention Tetraniliprole 80.0 80.0 80.0 Morwet ® IP 2.4 2.4 2.4 Atlox 4913 9.4 9.4 9.4 Synperonic PE/F 127 3.5 4.4 3.5 Radia 7130 0.0 10.6 0.0 Polyox WSR N12K 0.0 0.0 21.0 Antarox B/848 0.0 52.0 0.0 Crovol CR70 0.0 0.0 52.0 Licomer ® ADH205 0.0 31.0 0.0 Atplus FA 0.0 0.0 60.0 Rhodopol 23 3.5 3.5 3.5 Proxel ® GXL 1.5 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 0.8 Propylene Glycol 52.0 52.0 52.0 SAG ® 1572 2.0 2.0 2.0 Citric Acid 1.0 1.0 1.0 Water (add to 1 litre) To volume To volume To volume

The method of preparation used was according to Method 1 (IN21, IN25), and according to Method 2 (IN85)

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN2.2 Leaf wash-off data. Amount of deposit remaining after 1 h Recipe on corn leaves Recipe IN21 not according to ++ the invention—10 l/ha Recipe IN21 not according to +++ the invention—200 l/ha Recipe IN25 according to the +++++ invention—10 l/ha Recipe IN25 according to the ++++ invention—200 l/ha Recipe IN85 according to the +++ invention—10 l/ha Recipe IN85 according to the +++ invention—200 l/ha Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipes IN25, and IN85 illustrative of the invention show a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipe IN21.

Example IN3: Imidacloprid+Thiacloprid 300 SC

TABLE IN3.1 Recipes IN31 and IN35 Recipe Recipe IN35 IN31 according to Component (g/l) reference the invention Imidacloprid 150.0 150.0 Thiacloprid 150.0 150.0 Morwet ® D425 5.0 5.0 Atlox 4913 30.0 30.0 Soprophor TS54 10.0 10.0 Exxsol D80 0.0 20.0 Synperonic PE/F 127 0.0 2.0 Lucramul HOT 5902 0.0 70.0 Atplus FA 0.0 60.0 Rhodopol 23 2.0 2.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 Glycerine 80.0 80.0 SAG ® 1572 2.0 2.0 Citric Acid 1.0 1.0 Water (add to 1 litre) To volume To volume

The method of preparation used was according to Method 1.

Pipette Spreading Tests on Leaves

The leaf deposit size was determined according to method 17.

TABLE IN3.2 Spray dilution droplet size and dose on non-textured apple leaves and textured rice leaves. Deposit Deposit Spreading Spreading area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple rice g/ha % w/v Recipe IN31 not 3,610 7,570 0 0 according to the invention—8 l/ha Recipe IN31 not 3,280 5,690 0 0 according to the invention—15 l/ha Recipe IN31 not 4,750 9,050 0 0 according to the invention—100 l/ha Recipe IN35 according 4,240 5,750 0 0 to the invention—8 l/ha Recipe IN35 according to 4,390 5,610 0 0 the invention—15 l/ha Recipe IN35 according to 6,070 7,380 0 0 the invention—100 l/ha

Formulations applied at 8/15/100 l/ha.

The results show that recipe IN32 illustrative of the invention shows greater deposit sizes at 8 and 15 L/ha spray volume than at 100 L/ha and also compared to the reference recipe IN31.

Cuticle Penetration

The penetration through apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE IN3.3 Cuticle penetration of Imidacloprid for Imidacloprid + Thiacloprid SC formulations. Uptake enhancing Uptake enhancing agent Penetration % Penetration % agent dose dose in spray liquid Recipe 25-27 h 45-47 h g/ha % w/v Recipe IN31 not according 18.7 25.5 0 0 to the invention—10 l/ha Recipe IN31 not according 7.0 8.4 0 0 to the invention—200 l/ha Recipe IN35 according to 52.5 67.0 35 0.35 the invention—10 l/ha Recipe IN35 according to 14.1 16.8 35 0.0175 the invention—200 l/ha

Formulations tested at 0.5 l/ha.

The results show that recipe IN35 illustrative of the invention has a higher cuticle penetration than the reference recipe IN31 at both 10 l/ha and 200 l/ha. Furthermore, recipe IN35 has a higher penetration at 10 l/ha compared to 200 l/ha.

TABLE IN3.4 Cuticle penetration of Thiacloprid for Imidacloprid + Thiacloprid SC formulations. Uptake enhancing Uptake enhancing agent Penetration % Penetration % agent dose dose in spray liquid Recipe 25-27 h 45-47 h g/ha % w/v Recipe IN31 not according 1.7 2.7 0 0 to the invention—10 l/ha Recipe IN31 not according 0.0 0.1 0 0 to the invention—200 l/ha Recipe IN35 according to 10.5 13.6 35 0.35 the invention—10 l/ha Recipe IN35 according to 3.9 5.7 35 0.0175 the invention—200 l/ha

Formulations tested at 0.5 l/ha.

The results show that recipe IN35 illustrative of the invention has a higher cuticle penetration than the reference recipe IN31 at both 10 l/ha and 200 l/ha. Furthermore, recipe IN35 has a higher penetration at 10 l/ha compared to 200 l/ha.

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN3.5 Leaf wash-off data. Amount of deposit remaining after 1 h Recipe on corn leaves Recipe IN31 not according to ++ the invention—10 l/ha Recipe IN31 not according to +++ the invention—200 l/ha Recipe IN35 according to the +++ invention—10 l/ha Recipe IN35 according to the ++++ invention—200 l/ha Formulations tested at 0.5 l/ha (+ = all washed-off, +++++ = all remaining)

The results show that recipe IN35 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha & 200 L/ha spray volume compared to the reference recipe IN35.

Example IN4: Deltamethrin 25 SC

TABLE IN 4.1 Recipes IN41 and IN45 Recipe Recipe IN45 IN41 according to Component (g/l) reference the invention Deltamethrin 25.0 25.0 Soprophor TS29 20.0 20.0 Marcol 82 0.0 30.0 Synperonic PE/F 127 0.0 3.0 Genapol C100 0.0 70.0 Licomer ADH205 0.0 60.0 Rhodopol 23 2.0 2.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 Glycerine 80.0 80.0 SAG ® 1572 2.0 2.0 Citric Acid 1.0 1.0 Water (add to 1 litre) To volume To volume

The method of preparation used was according to Method 1.

Pipette Spreading Tests on Leaves

The leaf deposit size was determined according to method 17.

TABLE IN4.2 Spray dilution droplet size and dose on non-textured apple leaves and textured rice leaves. Deposit Deposit Spreading Spreading area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple rice g/ha % w/v Recipe IN41 not 5.21 1.19 0 0 according to the invention—8 l/ha Recipe IN41 not 4.63 0.95 0 0 according to the invention—15 l/ha Recipe IN41 not 5.47 2.29 0 0 according to the invention—100 l/ha Recipe IN45 according 5.05 1.76 0 0 to the invention—8 l/ha Recipe IN45 according 4.81 2.14 0 0 to the invention—15 l/ha Recipe IN45 according 5.91 1.89 0 0 to the invention—100 l/ha

Formulations applied at 8/15/100 l/ha.

The results show that recipe IN45 illustrative of the invention shows greater deposit sizes at 8 & 15 L/ha spray volume on rice than at 100 L/ha and also compared to the reference recipe IN41.

Example IN5: Ethiprole 200 SC

TABLE IN 5.1 Recipes IN51 and IN55 Recipe Recipe IN55 IN51 according to Component (g/l) reference the invention Ethiprole 200.0 200.0 Soprophor FLK 30.0 30.0 Rapeseed Oil 0.0 30.0 Synperonic PE/F 127 0.0 3.0 Alkamuls A 0.0 70.0 Atplus FA 0.0 60.0 Rhodopol 23 2.0 2.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 Glycerine 80.0 80.0 SAG ® 1572 2.0 2.0 Citric Acid 1.0 1.0 Water (add to 1 litre) To volume To volume

The method of preparation used was according to Method 1.

Pipette Spreading Tests on Leaves

The leaf deposit size was determined according to method 17.

TABLE IN5.2 Spray dilution droplet size and dose on non-textured apple leaves and textured rice leaves. Deposit Deposit Spreading Spreading area area agent agent dose in mm{circumflex over ( )}2 mm{circumflex over ( )}2 dose spray liquid Recipe apple rice g/ha % w/v Recipe IN51 not according 3,310 1,560 0 0 to the invention—8 l/ha Recipe IN51 not according 2,540 2,300 0 0 to the invention—15 l/ha Recipe IN51 not according 3.9 2,290 0 0 to the invention—100 l/ha Recipe IN55 according to 5,640 7,380 0 0 the invention—8 l/ha Recipe IN55 according to 3,180 3,730 0 0 the invention—15 l/ha Recipe IN55 according to 4,570 2,870 0 0 the invention—100 l/ha

Formulations applied at 8/15/100 l/ha.

The results show that recipe IN52 illustrative of the invention shows greater deposit sizes at 8 and 15 L/ha spray volume than at 100 L/ha and also compared to the reference recipe IN51.

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN5.3 Leaf wash-off data. Amount of deposit remaining after 1 h Recipe on corn leaves Recipe IN51 not according to ++ the invention—10 l/ha Recipe IN51 not according to +++ the invention—200 l/ha Recipe IN55 according to the +++ invention—10 l/ha Recipe IN55 according to the ++++ invention—200 l/ha Formulations tested at 0.5 l/ha (+ = all washed-off, +++++ = all remaining)

The results show that recipe IN55 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha & 200 L/ha spray volume compared to the reference recipe IN51.

Example IN6: Flupyradifurone 150 SC

TABLE IN6.1 Recipes IN61 and IN65 Recipe Recipe IN65 IN61 according to Component (g/l) reference the invention Flupyradifurone 150.0 150.0 Atlox 4894 11.0 11.0 Atlox 4913 48.0 48.0 Crodamol OP 0.0 30.0 Synperonic PE/F 127 0.0 3.0 Antarox B/848 0.0 50.0 Licomer ® ADH205 0.0 20.0 Rhodopol 23 2.0 2.0 Aerosil R972 6.0 6.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 Urea 70.0 70.0 SAG ® 1572 1.0 1.0 Citric Acid 0.2 0.2 Water (add to 1 litre) To volume To volume

The method of preparation used was according to Method 1.

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN6.2 Leaf wash-off data. Amount of deposit remaining after Recipe 1 h on corn leaves Recipe IN61 not according to the invention-10 l/ha ++ Recipe IN61 not according to the invention-200 +++ l/ha Recipe IN65 according to the invention-10 l/ha ++ Recipe IN65 according to the invention-200 l/ha ++++ Formulations tested at 0.5 l/ha (+ = all washed-off, +++++ = all remaining)

The results show that recipe IN65 illustrative of the invention shows a higher amount of applied formulation remaining at 200 L/ha spray volume compared to the reference recipe IN61.

Example IN7: Spidoxamat 48 SC

TABLE IN 7.1 Recipes IN71 and IN75 Recipe Recipe IN75 IN71 according to Component (g/l) reference the invention Spidoxamat 48.0 48.0 Soprophor TS54 15.0 15.0 Atlox 4913 45.0 45.0 Rapeseed Oil Methyl ester 0.0 20.0 Synperonic PE/F 127 0.0 2.0 Antarox B/848 0.0 50.0 Licomer ® ADH205 0.0 20.0 Rhodopol 23 2.0 2.0 Citric Acid 0.2 0.2 Glycerine 100.0 100.0 Proxel ® GXL 1.5 1.5 Kathon ® CG/ICP 0.8 0.8 SAG ® 1572 1.0 1.0 Water To volume To volume

The method of preparation used was according to Method 1.

Leaf Wash-Off

The wash-off was determined according to method 15, but with a wash off rate of 600 mL/min

TABLE IN7.2 Leaf wash-off data. Amount of deposit remaining after Recipe 1 h on corn leaves Recipe IN71 not according to the invention-10 l/ha ++ Recipe IN71 not according to the invention-200 +++ l/ha Recipe IN75 according to the invention-10 l/ha ++++ Recipe IN75 according to the invention-200 l/ha +++++ Formulations tested at 0.5 l/ha (+ = all washed-off, ++++ = all remaining)

The results show that recipe IN75 illustrative of the invention shows a higher amount of applied formulation remaining at 10 & at 200 L/ha spray volume compared to the reference recipe IN71.

Herbicide Examples

Example HB1.1: Triafamone 100 SC

TABLE HB1.1 Recipes HB1.1, HB1.2 and HB1.3. Recipe Recipe HB1.2 HB1.1 according to Recipe HB1.3 Component (g/l) reference the invention reference TRIAFAMONE 100.0 100.0 100.0 Synperonic ® PE/F127 10.8 10.8 10.8 Atlox ® 4913 32.4 32.4 32.4 Atlox ® 44894 21.6 21.6 21.6 Polyox ® WSR N60K 0.0 0.8 0.0 Genapol ® X0 60 0.0 80 80 Licomer ® ADH205 0.0 65 65 Xanthan gum 0.4 0.4 0.4 Proxel ® GXL 1.8 1.8 1.8 Kathon ® CG/ICP 0.8 0.8 0.8 Propylene glycol 54 54 54 Silcolapse ® 545 0.2 0.2 0.2 Na2HPO4 (Buffer solution 1.5 1.5 1.5 pH = 7) NaH2PO4 (Buffer solution 0.8 0.8 0.8 pH = 7) Water (add to 1 litre) To volume To volume To volume (~850) (~704) (~705)

The method of preparation used was according to Method 2.

Drift

The drift was determined according to method 7.

TABLE HB1.2 Drift data. Relative amount Relative amount of driftable of driftable fraction of spray fraction of spray droplets < 100 droplets < 150 Concentration microns from microns from Concentration of drift recipe HB1.2 recipe HB1.2 of drift reducing oil Dose of drift Spray compared to compared to reducing oil (b) in spray reducing oil volume recipe HB1.3 recipe HB1.3 (b) in recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 10 92.9 100 0.8 0.0004 0.4 Formulations tested at 0.5 l/ha.

Formulations tested at 0.5 l/ha.

The results show that recipes HB1.2 illustrative of the invention shows a lower amount of driftable fraction of spray droplets less than 150 microns at 10 l/ha spray volume compared to the reference recipe HB1.3 without drift reducing additive (b).

TABLE HB1.3 Drift data. Relative amount Relative amount of driftable of driftable fraction of spray fraction of spray droplets < 100 droplets < 150 Concentration microns from microns from Concentration of drift recipe HB1.2 recipe HB1.2 of drift reducing oil Dose of drift Spray compared to compared to reducing oil (b) in spray reducing oil volume recipe HB1.3 recipe HB1.3 (b) in recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 20 58.3 71.7 0.8 0.0002 0.4 Formulations tested at 0.5 l/ha.

Formulations tested at 0.5 l/ha.

The results show that recipes HB1.2 illustrative of the invention shows a lower amount of driftable fraction of spray droplets less than 150 microns at 20 l/ha spray volume compared to the reference recipe HB1.3 without drift reducing additive (b).

Cuticle Penetration

The penetration through apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE HB1.4 Cuticle penetration for Triafamone SC formulations. Uptake enhancing agent Uptake enhancing agent Penetration % dose dose in spray liquid Recipe 46-47 h g/ha % w/v Recipe HB1.1 not according 28.6 0 0 to the invention-10 l/ha Recipe HB1.1 not according 22.4 0 0 to the invention-200 l/ha Recipe HB1.2 according to 68.6 40 0.4 the invention-10 l/ha Recipe HB1.2 according to 30.5 40 0.02 the invention-200 l/ha Formulations tested at 0.5 l/ha.

Formulations tested at 0.5 l/ha.

The results show that recipe HB1.2 illustrative of the invention has a higher cuticle penetration than the reference recipe HB1.1 at both 10 l/ha and 200 l/ha. Furthermore, recipe HB1.2 has a higher penetration at 10 l/ha compared to 200 l/ha.

Leaf Wash-Off

TABLE HB1.5 Leaf wash-off data. Amount of deposit remaining after 1 h on corn leaves Recipe HB1.1 not according to the invention-10 l/ha + Recipe HB1.2 according to the invention-10 l/ha +++ Recipe HB1.1 not according to the invention-200 l/ha ++ Recipe HB1.2 according to the invention-200 l/ha ++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe HB1.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha and 200 L/ha spray volume compared to the reference recipes HB1.1.

Example HB2: Tembotrione+Isoxadifen 315 SC

TABLE HB2.1 Recipes HB2.1 and HB2.2 Recipe Recipe HB2.2 HB2.1 according to Component (g/l) reference the invention TEMBOTRIONE 210.00 210.00 ISOXADIFEN-ETHYL 105.00 105.00 Atlox ® 4913 37.00 37.00 Atlas ® G 5000 12.00 12.00 SYNPERONIC ® A7 12.00 12.00 Rapeseed oil methyl ester 0.00 14.00 Genapol ® X0 90 0.00 60.00 Licomer ® ADH205 0.00 60.00 1.2-Propylene glycol 61.00 61.00 Silcolapse ® 482 2.50 2.50 Acticide ® MBS 2.50 2.50 Xanthan gum 2.00 2.00 Water (add to 1 litre) To volume To volume (~761) (~607)

The method of preparation used was according to Method 1.

Cuticle Penetration

The penetration through apple leaf cuticles was determined according to cuticle penetration test method 13.

TABLE HB2.2 Cuticle penetration for Tembotrione SC formulations. Uptake enhancing agent Uptake enhancing agent Penetration % dose dose in spray liquid Recipe 43-45 h g/ha % w/v Recipe HB2.1 not according 0.9 0 0 to the invention-10 l/ha Recipe HB2.1 not according 0.2 0 0 to the invention-200 l/ha Recipe HB2.2 according to 5.7 30 0.3 the invention-10 l/ha Recipe HB2.2 according to 0.7 30 0.015 the invention-200 l/ha Formulations tested at 0.5 l/ha.

Formulations tested at 0.5 l/ha.

The results show that recipe HB2.2 illustrative of the invention has a higher cuticle penetration than the reference recipe HB2.1 at both 10 l/ha and 200 l/ha. Furthermore, recipe HB2.2 has a higher penetration at 10 l/ha compared to 200 l/ha.

Leaf Wash-Off

TABLE HB2.3 Leaf wash-off data. Amount of deposit remaining after 1 h on corn leaves Recipe HB2.1 not according to the invention-10 l/ha +++ Recipe HB2.2 according to the invention-10 l/ha ++++ Recipe HB2.1 not according to the invention-200 l/ha ++++ Recipe HB2.2 according to the invention-200 l/ha +++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe HB2.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha and 200 L/ha spray volume compared to the reference recipes HB2.1.

Example HB3: Thiencarbazone+Cyprosulfamide 200 SC

TABLE HB3.1 Recipes HB3.1, HB3.2 and HB3.3 Recipe Recipe HB3.2 HB3.1 according to Recipe HB3.3 Component (g/l) reference the invention reference Thiencarbazone-methyl 100.00 100.00 100.00 Cyrosulfamide 100.00 100.00 100.00 Dispersogen ® LFH 50.00 50.00 50.00 Multitrope ® 1620 12.00 12.00 12.00 Rapeseed oil methyl ester 0.00 14.00 14.00 Silwet ® HS-312 0.00 0.00 0.00 Genapol ® X0 90 0.00 60.00 60.00 Licomer ® ADH205 0.00 60.00 0.00 1.2-Propylene glycol 80.00 80.00 80.00 Silcolapse ® 416 3.00 3.00 3.00 Procel ® GLX 1.20 1.20 1.20 Xanthan gum 3.50 3.50 3.50 Water (add to 1 litre) To volume To volume To volume The method of preparation used was according to Method 1.

The method of preparation used was according to Method 1.

Drift

The drift was determined according to method 7.

TABLE HB3.2 Drift data. Relative amount Relative amount of driftable of driftable fraction of spray fraction of spray droplets < 100 droplets < 150 Concentration microns from microns from Concentration of drift recipe HB3.2 recipe HB3.2 of drift reducing oil Dose of drift Spray compared to compared to reducing oil (b) in spray reducing oil volume recipe HB3.3 recipe HB3.3 (b) in recipe liquid (b) in target l/ha % % g/l % w/v crop g/ha 20 95.5 91.2 0.8 0.0002 0.4 Formulations tested at 0.5 l/ha.

Formulations tested at 0.5 l/ha.

The results show that recipes HB3.2 illustrative of the invention shows a lower amount of driftable fraction of spray droplets less than 100 microns and less than 150 microns at 20 l/ha spray volume compared to the reference recipe HB3.3 without drift reducing additive (b).

Leaf Wash-Off

TABLE HB3.3 Leaf wash-off data. Amount of deposit remaining after Recipe DUR 1 h on corn leaves Recipe HB3.1 not according to the invention-10 l/ha ++ Recipe HB3.2 according to the invention-10 l/ha ++++ Recipe HB3.1 not according to the invention-200 l/ha ++++ Recipe HB3.2 according to the invention-200 l/ha ++++ Formulations tested at 0.5 l/ha. (+ = all washed-off, +++++ = all remaining)

The results show that recipe HB3.2 illustrative of the invention shows a higher amount of applied formulation remaining at 10 L/ha spray volume compared to the reference recipes HB3.1.

Claims

1. An agrochemical formulation comprising comprising the components a) to g) in the following amounts

a) One or more active ingredients,
b) One or more drift reducing ingredients
d) One or more uptake enhancing agents,
e) One or more rain-fast additives,
f) Optional other formulants,
g) one or more carriers to volume,
a) from 5 to 500 g/l,
b) from 0.01 to 50 g/l, and in case of b) being an vegetable oil or ester from in 1 to 50 g/l, in case of b) being a drift reducing polymer in 0.05 to 3 g/l,
d) from 10 to 180 g/l,
e) from 5 to 150 g/l,
g) carrier to volume.

2. The agrochemical formulation according to claim 1, wherein component f) is mandatory and present in at least one of

f1) from 8 to 120 g/l,
f2) from 1 to 20 g/l,
f3) from 0.5 to 20 g/l,
f4) from 5 to 150 g/l,
f5) from 0.1 to 120 g/l,

3. The agrochemical formulation according to claim 1, wherein b) is selected from the group comprising poly(ethylene) oxides with an average molecular weight optionally from 0.5 to 12 million g/mol, optionally from 0.75 to 10 million g/mol, and optionally from 1 to 8 million g/mol, and vegetable oils and vegetable oil esters and diester including esters with glycerine and propylene glycol.

4. The agrochemical formulation according to claim 1, wherein b) is selected from the group comprising a polymer selected from the group consisting of hydroxypropyl guar and poly(ethylene) oxides with an average molecular weight optionally from 0.5 to 12 million g/mol, optionally from 0.75 to 10 million g/mol, and optionally from 1 to 8 million g/mol, and is present in 0.05 to 10 g/l, optionally from 0.1 to 8 g/l, and optionally from 0.2 to 6 g/l., optionally a poly (ethylene oxide).

5. The agrochemical formulation according to claim 1, wherein b) is selected from the group comprising vegetable oils and vegetable oil esters and diester including esters with glycerine and propylene glycol and is present 1 to 50 g/l, optionally from 5 to 30 g/l, and optionally from 6 to 30 g/l.

6. The agrochemical formulation according to claim 1, wherein d) is selected from the group comprising ethoxylated alcohols, propoxy-ethoxylated alcohols, ethoxylated carboxylic acids, propoxy-ethoxylated carboxylic acids, or ethoxylated mono-, di- or triesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 5-40 EO units.

7. The agrochemical formulation according to claim 1, wherein e) is an emulsion polymer or polymer dispersion with Tg in the range from −100° C. to 30° C., wherein said polymer is a copolymer of an acrylate and a styrene, wherein said acrylate is selected from the group consisting of 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof, and said styrene is selected from the group consisting of styrene, tert-butyl styrene, para-methyl styrene, or combinations thereof.

8. The agrochemical formulation according to claim 1, wherein a) is present from 10 to 320 g/l, and optionally from 20 to 230 g/l.

9. The agrochemical formulation according to claim 1, wherein d) is present from 20 to 150 g/l, and optionally from 30 to 140 g/l.

10. The agrochemical formulation according to claim 1, wherein e) is present from 10 to 100 g/l, and optionally from 20 to 80 g/l.

11. The agrochemical formulation according to claim 1, wherein b) is capable of being applied from 0.1 g/ha to 50 g/ha, optionally from 1 g/ha to 40 g/ha, and optionally from 5 g/ha to 30 g/ha.

12. The agrochemical formulation according to claim 1, wherein b) is capable of being applied from 0.01 g/ha to 25 g/ha, optionally from 0.05 g/ha to 10 g/ha, and optionally from 0.1 g/ha to 6 g/ha.

13. The agrochemical formulation according to claim 1, wherein the active ingredient is selected from the group consisting of trifloxystrobin, bixafen, prothioconazole, inpyrfluxam, isoflucypram, fluopicolide, fluopyram, fluoxapiprolin, isotianil, spirotetramat, tetraniliprole, ethiprole, imidacloprid, deltamethrin, flupyradifuron, spidoxamat, triafamone, tembotrione, thiencarbazone-methyl, isoxadifen-ethyl and cyprosulfamat.

14. The agrochemical formulation according to claim 1, wherein component f) comprises at least one non-ionic surfactant and/or ionic surfactant (f1), one rheological modifier (f2), and one antifoam substance (f3) and at least one antifreeze agent (f4).

15. The agrochemical formulation according to claim 1, comprising the components a) to g) in the following amounts

a) y from 10 to 320 g/l, and optionally from 20 to 230 g/l,
b) from 0.1 to 30 g/l, and optionally from 1 to 20 g/l, and in case of b) being an vegetable oil or ester from from 5 to 30 g/l, and optionally from 6 to 30 g/l, in case of b) being a drift reducing polymer from 0.1 to 2 g/l, and optionally from 0.2 to 1.5 g/l
d) from 20 to 150 g/l, and optionally from 30 to 140 g/l,
e) 10 to 100 g/l, and optionally from 20 to 80 g/l,
f1) from 8 to 120 g/l, and optionally from 10 to 80 g/l,
f2) from 1 to 20 g/l, and optionally from 2 to 10 g/l,
f3) from 0.5 to 20 g/l, and optionally from 1 to 12 g/l,
f4) from 5 to 150 g/l, and optionally from 10 to 120 g/l,
f5) from 0.1 to 120 g/l, and optionally from 0.5 to 80 g/l,
g) carrier to volume.

16. The agrochemical formulation according to claim 1, wherein the formulation is applied at a spray volume of between 1 and 30 I/ha, optionally 1 and 20 I/ha, optionally between 2 and 15 l/ha, and optionally 5 and 15 l/ha.

17. The agrochemical formulation according to claim 1, wherein the formulation is an in-can formulation.

18. The agrochemical formulation according to claim 1, wherein the concentration of additives b) to e) in a spray liquid thereof is from

Additive b) from 0.005 to 1 g/l, and optionally from 0.04 to 0.6 g/l where b) is a polymer
Additive b) from 0.01 to 5 g/l, and optionally from 0.02 to 2.5 g/l where b) is an oil
Additive d) from 1 to 20 g/l, and optionally from 2 to 8 g/l
Additive e) from 0.5 to 10 g/l, and optionally from 2 to 6 g/l.

19. The agrochemical formulation according to claim 1, wherein dose of additives b) to e) per ha is from

Additive b) from 0.05 to 10 g/ha, and optionally from 0.4 to 6 g/ha where b) is a polymer
Additive b) from 0.1 to 50 g/ha, and optionally from 0.2 to 30 g/ha where b) is an oil
Additive d) from 10 to 200 g/ha, and optionally from 40 to 80 g/ha
Additive e) from 5 to 100 g/ha, and optionally from 20 to 60 g/ha.

20. The agrochemical formulation according to claim 1, wherein the concentration in the formulation, the concentration in a spray liquid thereof and dose of additives b) to e) per ha is combined in the following way

Additive b) from 0.4 to 6 g/l in the formulation, from 0.02 to 0.6 g/l in the spray liquid and from 0.2 to 6 g/ha where b) is a polymer
Additive b) from 0.1 to 50 g/l in the formulation, from 0.01 to 5 g/l in the spray liquid and from 0.2 to 30 g/ha where b) is an oil
Additive d) from 40 to 160 g/l in the formulation, from 2 to 8 g/l in the spray liquid and from to 80 g/ha
Additive e) from 20 to 80 g/l in the formulation, from 1 to 6 g/l in the spray liquid and from to 60 g/ha.

21. A method of applying an agrochemical formulation according to claim 1 onto crops, comprising applying the formulation at a spray volume of between 1 and 30 l/ha, optionally 1 and 20 l/ha, optionally between 2 and 15 l/ha, and optionally 5 and 15 l/ha.

22. A product comprising an agrochemical formulation according to to claim 1 adapted for application of one or more agrochemical compounds for controlling harmful organisms, wherein the formulation is capable of being is applied by a UAV, UGV, PWM.

Patent History
Publication number: 20240032532
Type: Application
Filed: Nov 5, 2021
Publication Date: Feb 1, 2024
Inventors: Malcolm Andrew FAERS (Duesseldorf), Jun DONG (Leverkusen), Arno RATSCHINSKI (Duesseldorf), Gorka PERIS URQUIJO (Koeln), Oliver GAERTZEN (Koeln), Emilia HILZ (Haan), Sybille LAMPRECHT (Leverkusen)
Application Number: 18/251,506
Classifications
International Classification: A01N 25/06 (20060101); A01N 25/24 (20060101); A01N 37/50 (20060101); A01N 43/56 (20060101); A01N 43/40 (20060101); A01N 43/653 (20060101); A01N 43/80 (20060101); A01P 7/04 (20060101); A01N 43/713 (20060101); A01N 43/50 (20060101); A01N 47/40 (20060101); A01N 53/00 (20060101); A01N 43/90 (20060101); A01N 43/88 (20060101); A01P 13/00 (20060101); A01N 41/10 (20060101); A01N 47/38 (20060101); A01N 37/28 (20060101); A01P 3/00 (20060101);